Organic semiconductor element, manufacturing method thereof, organic semiconductor composition, and organic semiconductor film

ABSTRACT

Objects of the present invention are to provide an organic semiconductor element having excellent coating manufacturing process suitability, excellent carrier mobility, excellent heat resistance, and excellent flexibility of a semiconductor active layer and to provide an organic semiconductor composition that can form an organic semiconductor having excellent coating manufacturing process suitability, excellent carrier mobility, excellent heat resistance and excellent flexibility, an organic semiconductor film in which the composition is used, and a method of manufacturing an organic semiconductor element. 
     The organic semiconductor element according to the present invention includes a compound represented by Formula 1 in a semiconductor active layer. In Formula 1, A is an aromatic ring selected from any one of aromatic rings represented by Formula 2 or 3, *&#39;s represent bonding positions to two side chalcogenophene rings, X a &#39;s represent chalcogen atoms, one of X 1  and Y 1  is a chalcogen atom, and one of X 2  and Y 2  is a chalcogen atom.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of International Application No.PCT/JP2015/084494 filed on Dec. 9, 2015, which claims priority toJapanese Patent Application No. 2014-253805 filed on Dec. 16, 2014. Theentire contents of these applications are incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an organic semiconductor element, amanufacturing method thereof, an organic semiconductor composition, andan organic semiconductor film.

2. Description of the Related Art

An organic transistor having an organic semiconductor film(semiconductor active layer) is used in a field effect transistor (FET)used in a liquid crystal display or an organic electroluminescence (EL)display, a radio frequency identifier (RFID, RF Tag), and the like,because lightening of weight, cost reduction, and flexibilization can beachieved.

As an organic transistor material in the related art, those disclosed inJP2009-54810A, JP2010-177642A, and JP2009-190999A are known.

SUMMARY OF THE INVENTION

An object to be achieved by the present invention is to provide anorganic semiconductor element having excellent coating manufacturingprocess suitability, excellent carrier mobility, excellent heatresistance, and flexibility of a semiconductor active layer.

Another object to be achieved by the present invention is to provide anorganic semiconductor composition that can form an organic semiconductorhaving excellent coating manufacturing process suitability, excellentcarrier mobility, excellent heat resistance, and excellent flexibility,and an organic semiconductor film in which the composition is used, anda method of manufacturing an organic semiconductor element.

The object of the present invention is solved by the means described in<1>, <15>, <17>, or <18> below. <2> to <14>, and <16> which arepreferable embodiments are also described below.

<1> An organic semiconductor element comprising: a compound representedby Formula 1 below in a semiconductor active layer,

in Formula 1, A represents a central aromatic ring and is an aromaticring selected from any one of aromatic rings represented by Formula 2 or3, *'s represent bonding positions to two side chalcogenophene rings,and X^(a)'s represent chalcogen atoms,

one of X¹ and Y¹ is a chalcogen atom and the other is C(R^(a)), one ofX² and Y² is a chalcogen atom and the other is C(R^(b)), R^(a)'s eachindependently represent a hydrogen atom or R¹, R^(b)'s eachindependently represent a hydrogen atom or R², in a case where A is anaromatic ring represented by Formula 3, Y¹ and Y² are each independentlya chalcogen atom, X¹ is C(R^(a)), and X² is C(R^(b)), p and q eachindependently represent an integer of 0 to 2, Z's each independentlyrepresent a hydrogen atom or a halogen atom, and R¹ and R² eachindependently represent a halogen atom or a group represented by FormulaW below,—S-L-T  (W)

in Formula W, S represents a single bond or —(C(R^(S))₂)_(n)—, R^(S)'seach independently represent a hydrogen atom or a halogen atom, nrepresents an integer of 1 to 17, L represents a single bond, a divalentlinking group represented by any one of Formulae L-1 to L-15 below, or adivalent linking group obtained by bonding two or more divalent linkinggroups represented by any one of Formulae L-1 to L-15 below, and Trepresents an alkyl group, a haloalkyl group, a cyano group, a vinylgroup, an ethynyl group, an aryl group, a heteroaryl group, anoxyethylene group, an oligooxyethylene group in which a repetitionnumber of oxyethylene units is two or greater, a siloxane group, anoligosiloxane group having two or more silicon atoms, or a trialkylsilylgroup, and

in Formulae L-1 to L-15, a wavy line portion represents a bondingposition to S or another divalent linking group represented by any oneof Formulae L-1 to L-15, * represents a bonding position to T or anotherdivalent linking group represented by any one of Formulae L-1 to L-15, min Formula L-13 represents an integer of 0 to 4, m's in Formulae L-14and L-15 each represent an integer of 0 to 2, R″s in Formulae L-1 andL-2 each independently represent a hydrogen atom or a substituent, andR″'s in Formulae L-13, L-14, and L-15 each independently represent asubstituent.

<2> The organic semiconductor element according to <1>, in which both ofX¹ and X² are chalcogen atoms, or both of Y¹ and Y² are chalcogen atoms.

<3> The organic semiconductor element according to <1> or <2>, in whichZ is a hydrogen atom.

<4> The organic semiconductor element according to any one of <1> to<3>, in which p and q are each independently 1 or 2.

<5> The organic semiconductor element according to any one of <1> to<4>, in which both of p and q are 1.

<6> The organic semiconductor element according to <5>, in whichsubstitution positions of R¹ and R² are respectively second positions ofterminal chalcogenophene rings.

<7> The organic semiconductor element according to any one of <1> to<6>, in which X^(a) is a S atom.

<8> The organic semiconductor element according to any one of <1> to<7>, in which both of two terminal chalcogenophene rings in Formula 1are thiophene rings.

<9> The organic semiconductor element according to any one of <1> to<8>, in which a sum of the numbers of carbon atoms in the grouprepresented by Formula W is 4 to 40.

<10> The organic semiconductor element according to any one of <1> to<9>, in which L is a divalent linking group represented by any one ofFormulae L-1 to L-4 and L-13 to L-15, or a divalent linking groupobtained by bonding two or more divalent linking groups represented byany one of Formulae L-1 to L-4 and L-13 to L-15.

<11> The organic semiconductor element according to any one of <1> to<10>, in which L is a divalent linking group represented by any one ofFormulae L-1 to L-4 and L-13 to L-15 singly.

<12> The organic semiconductor element according to any one of <1> to<11>, in which T is an alkyl group.

<13> The organic semiconductor element according to any one of <1> to<12>, in which W is an alkyl group.

<14> The organic semiconductor element according to any one of <1> to<13>, which is an organic thin film transistor.

<15> An organic semiconductor composition comprising: a compoundrepresented by Formula 1 below; and a solvent having a boiling point of100° C. or higher, in which a content of the compound represented byFormula 1 is 20 mass % or less with respect to a total amount of theorganic semiconductor composition,

in Formula 1, A represents a central aromatic ring and is an aromaticring selected from any one of aromatic rings represented by Formula 2 or3, *'s represent bonding positions to two side chalcogenophene rings,and X^(a)'s represent chalcogen atoms,

one of X¹ and Y¹ is a chalcogen atom and the other is C(R^(a)), one ofX² and Y² is a chalcogen atom and the other is C(R^(b)), R^(a)'s eachindependently represent a hydrogen atom or R¹, R^(b)'s eachindependently represent a hydrogen atom or R², in a case where A is anaromatic ring represented by Formula 3, Y¹ and Y² are each independentlya chalcogen atom, X¹ is C(R^(a)), and X² is C(R^(b)),

p and q each independently represent an integer of 0 to 2, Z's eachindependently represent a hydrogen atom or a halogen atom, and R¹ and R²each independently represent a halogen atom or a group represented byFormula W below,—S-L-T  (W)

in Formula W, S represents a single bond or an alkylene group—(C(R^(S))₂)_(n)—, R^(S)'s each independently represent a hydrogen atomor a halogen atom, n represents an integer of 1 to 17, L represents asingle bond, a divalent linking group represented by any one of FormulaeL-1 to L-15 below, or a divalent linking group obtained by bonding twoor more divalent linking groups represented by any one of Formulae L-1to L-15 below, and T represents an alkyl group, a haloalkyl group, acyano group, a vinyl group, an ethynyl group, an aryl group, aheteroaryl group, an oxyethylene group, an oligooxyethylene group inwhich a repetition number of oxyethylene units is two or greater, asiloxane group, an oligosiloxane group having two or more silicon atoms,or a trialkylsilyl group, and

in Formulae L-1 to L-15, a wavy line portion represents a bondingposition to S or another divalent linking group represented by any oneof Formulae L-1 to L-15, * represents a bonding position to T or anotherdivalent linking group represented by any one of Formulae L-1 to L-15, min Formula L-13 represents an integer of 0 to 4, m's in Formulae L-14and L-15 each represent an integer of 0 to 2, R″s in Formulae L-1 andL-2 each independently represent a hydrogen atom or a substituent, andR″'s in Formulae L-13, L-14, and L-15 each independently represent asubstituent.

<16> The organic semiconductor composition according to <15>, furthercomprising: a binder polymer, in which a content of the binder polymeris 0.001 to 10 mass % with respect to a total amount of the organicsemiconductor composition.

<17> A method of manufacturing an organic semiconductor element,comprising: an applying step of applying the organic semiconductorcomposition according to <15> or <16> to a substrate by an ink jetmethod or a flexographic printing method and a removing step of removingat least a portion of the solvent from the applied organic semiconductorcomposition.

<18> An organic semiconductor film formed from the organic semiconductorcomposition according to <15> or <16>.

According to the present invention, it is possible to provide an organicsemiconductor element having excellent coating manufacturing processsuitability, excellent carrier mobility, excellent heat resistance, andexcellent flexibility of a semiconductor active layer.

According to the present invention, it is possible to provide an organicsemiconductor composition that can form an organic semiconductor havingexcellent coating manufacturing process suitability, excellent carriermobility, excellent heat resistance, and excellent flexibility, and anorganic semiconductor film, and a method of manufacturing an organicsemiconductor element in which the composition is used.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of an aspect of an organicsemiconductor element of the present invention.

FIG. 2 is a schematic cross-sectional view of another aspect of theorganic semiconductor element of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the contents of the present invention will be specificallydescribed. The constituents in the following description will beexplained based on typical embodiments of the present invention, but thepresent invention is not limited to the embodiments. In thespecification of the present application, “to” is used to mean that thenumerical values listed before and after “to” are a lower limit and anupper limit respectively.

In the present specification, in a case where there is no descriptionregarding whether a group (atomic group) is substituted orunsubstituted, the group includes both of a group having a substituentand a group not having a substituent. For example, an “alkyl group”includes not only an alkyl group not having a substituent (unsubstitutedalkyl group) but also an alkyl group having a substituent (substitutedalkyl group).

In the present specification, in some cases, a chemical structuralformula is described as a simplified structural formula in which ahydrogen atom is omitted.

In the present invention, “mobility” refers to “carrier mobility” andmeans any one or both of electron mobility and hole mobility.

In the present invention, “mass %” and “weight %” have the samedefinition, and “part by mass” and “part by weight” have the samedefinition.

In the present invention, a combination of preferred aspects is morepreferable.

(Organic Semiconductor Element)

An organic semiconductor element according to the present inventionincludes a compound represented by Formula 1 below in a semiconductoractive layer.

In Formula 1, A represents a central aromatic ring and is an aromaticring selected from any one of aromatic rings represented by Formula 2 or3, *'s represent bonding positions to two side chalcogenophene rings,and X^(a)'s represent chalcogen atoms,

one of X¹ and Y¹ is a chalcogen atom and the other is C(R^(a)), one ofX² and Y² is a chalcogen atom and the other is C(R^(b)), R^(a)'s eachindependently represent a hydrogen atom or R¹, R^(b)'s eachindependently represent a hydrogen atom or R², in a case where A is anaromatic ring represented by Formula 3, Y¹ and Y² are each independentlya chalcogen atom, X¹ is C(R^(a)), and X² is C(R^(b)), and

p and q each independently represent an integer of 0 to 2, Z's eachindependently represent a hydrogen atom or a halogen atom, and R¹ and R²each independently represent a halogen atom or a group represented byFormula W below.—S-L-T  (W)

In Formula W, S represents a single bond or —(C(R^(S))₂)_(n)—, R^(S)'seach independently represent a hydrogen atom or a halogen atom, nrepresents an integer of 1 to 17, L represents a single bond, a divalentlinking group represented by any one of Formulae L-1 to L-15 below, or adivalent linking group obtained by bonding two or more divalent linkinggroups represented by any one of Formulae L-1 to L-15 below, and Trepresents an alkyl group, a haloalkyl group, a cyano group, a vinylgroup, an ethynyl group, an aryl group, a heteroaryl group, anoxyethylene group, an oligooxyethylene group in which a repetitionnumber of oxyethylene units is 2 or greater, a siloxane group, anoligosiloxane group having two or more silicon atoms, or a trialkylsilylgroup.

In Formulae L-1 to L-15, a wavy line portion represents a bondingposition to S or another divalent linking group represented by any oneof Formulae L-1 to L-15, * represents a bonding position to T or anotherdivalent linking group represented by any one of Formulae L-1 to L-15, min Formula L-13 represents an integer of 0 to 4, m's in Formulae L-14and L-15 each represent an integer of 0 to 2, R″s in Formulae L-1 andL-2 each independently represent a hydrogen atom or a substituent, andR″'s in Formulae L-13, L-14, and L-15 each independently represent asubstituent.

As a result of diligent research by the present inventors, the presentinventors have found that, if a compound represented by Formula 1 wascontained in a semiconductor active layer, it was possible to obtain anorganic semiconductor element having excellent coating manufacturingprocess suitability, excellent carrier mobility, excellent heatresistance, and excellent flexibility (flexible properties) of asemiconductor active layer, so as to complete the present invention.

The mechanism of exhibiting a specific effect is not clear. However, itis assumed that the effect of the present invention was exhibited sincea compound represented by Formula 1 had a specific fused polycyclicaromatic ring structure.

Hereinafter, an organic semiconductor element according to the presentinvention is described.

<Compound Represented by Formula 1>

The organic semiconductor element according to the present inventionincludes a compound represented by Formula 1 above in a semiconductoractive layer.

The compound represented by Formula 1 is an organic semiconductorcompound.

A represents a central aromatic ring and is an aromatic ring selectedfrom any one of aromatic rings represented by Formula 2 or 3, and *'srepresent bonding positions to two side chalcogenophene rings.

In view of mobility, A is preferably an aromatic ring represented byFormula 2.

X^(a) represents a chalcogen atom (an O atom, a S atom, a Se atom, and aTe atom), is preferably a S atom or a Se atom, and is more preferably aS atom. In the aforementioned aspect, carrier mobility of the obtainedorganic semiconductor film is more excellent.

One of X¹ and Y¹ is a chalcogen atom and the other is C(R^(a)), one ofX² and Y² is a chalcogen atom and the other is C(R^(b)), R^(a)'s eachindependently represent a hydrogen atom or R¹, R^(b)'s eachindependently represent a hydrogen atom or R², in a case where A is anaromatic ring represented by Formula 3, Y¹ and Y² are each independentlya chalcogen atom, X¹ is C(R^(a)), and X² is C(R^(b)).

It is preferable that both of X¹ and X² are chalcogen atoms, or both ofY¹ and Y² are chalcogen atoms.

X¹, Y¹, X², and Y² represent chalcogen atoms (O atoms, S atoms, Seatoms, and Te atoms), is preferably represent S atoms or Se atoms, andis more preferably represent S atoms. In the aforementioned aspect,carrier mobility of the obtained organic semiconductor film is moreexcellent.

In a case where A is an aromatic ring represented by Formula 2, it ispreferable that X¹ and X² are each independently a chalcogen atom, Y¹ isC(R^(a)), and Y² is C(R^(b)). In the aforementioned aspect, carriermobility of the obtained organic semiconductor film is more excellent.

Dotted lines in chalcogenophene rings of respective terminal representthat conjugated chains are formed.

p and q each independently represent an integer of 0 to 2, is preferably1 or 2, and is more preferably 1. In the aforementioned aspect, heatresistance and mobility of the obtained semiconductor active layer aremore excellent, and a domain size of an organic semiconductor at thetime of forming coating is excellent.

Z's each independently represent a hydrogen atom or a halogen atom andare preferably a hydrogen atom.

R¹ and R² each independently represent a halogen atom or a grouprepresented by Formula W below and is preferably a group represented byFormula W below. In the aforementioned aspect, carrier mobility of theobtained organic semiconductor film is more excellent.—S-L-T  (W)

S represents a single bond or —(C(R^(S))₂)_(n)— and is preferably asingle bond.

R^(S)'s each independently represent a hydrogen atom or a halogen atomand is preferably a hydrogen atom.

n represents an integer of 1 to 17, is preferably an integer of 1 to 8,and is more preferably an integer of 1 to 4.

In view of coating film formability, crystal sizes, and heat resistanceof the obtained organic semiconductor film, le and R² are preferably thesame groups.

The number of carbon atoms of R¹ is preferably 5 to 40 and morepreferably 8 to 20.

The number of carbon atoms of R² is preferably 5 to 40 and morepreferably 8 to 20.

L represents a single bond, a divalent linking group represented by anyone of Formulae L-1 to L-15 below, or a divalent linking group obtainedby bonding two or more divalent linking groups represented by any one ofFormulae L-1 to L-15 below. L is preferably a divalent linking grouprepresented by any one of Formulae L-1 to L-4 and L-13 to L-15 above ora divalent linking group obtained by bonding two or more divalentlinking groups represented by any one of Formulae L-1 to L-4 and L-13 toL-15 above and is more preferably a divalent linking group representedby any one of Formulae L-1 to L-4 and L-13 to L-15 above singly.

In Formulae L-1 to L-15, a wavy line portion represents a bondingposition to S or another divalent linking group represented by any oneof Formulae L-1 to L-15, * represents a bonding position to T or anotherdivalent linking group represented by any one of Formulae L-1 to L-15, min Formula L-13 represents an integer of 0 to 4, m's in Formulae L-14and L-15 each represent an integer of 0 to 2, R″s in Formulae L-1 andL-2 each independently represent a hydrogen atom or a substituent, andR″'s in Formulae L-13, L-14, and L-15 each independently represent asubstituent.

In a case where L represents a divalent linking group obtained bybonding two or more divalent linking groups represented by any one ofFormulae L-1 to L-15, * of one linking group is bonded to a wavy lineportion of another linking group.

A bonding position of R′ in Formulae L-13 to L-15 and a bondingposition * on a T side can be at arbitrary positions on an aromatic ringor a hetero aromatic ring.

The bonding position * on the T side in Formula L-13 can be at anarbitrary position on an aromatic ring.

R′ in Formulae L-1 and L-2 is preferably a hydrogen atom, a halogenatom, or an alkyl group and more preferably a hydrogen atom.

m's in Formulae L-13 to L-15 are preferably 0 or 1 and more preferably0.

As R″ in Formulae L-13 to L-15, a halogen atom, an alkyl group, analkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, oran aryl group is preferable.

T represents an alkyl group, a haloalkyl group, a cyano group, a vinylgroup, an ethynyl group, an aryl group, a heteroaryl group, anoxyethylene group, an oligooxyethylene group in which a repetitionnumber of oxyethylene units is 2 or greater, a siloxane group, anoligosiloxane group having two or more silicon atoms, or a trialkylsilylgroup, is preferably an alkyl group, a vinyl group, or an ethynyl group,is more preferably an alkyl group, is even more preferably an alkylgroup having 5 to 19 carbon atoms, and is particularly preferably analkyl group having 7 to 13 carbon atoms.

An alkyl group in T is preferably a linear alkyl group.

In the group represented by Formula W above, it is preferable that L isa methylene group, and T is an alkyl group. That is, the grouprepresented by Formula W above is preferably an alkyl group, morepreferably an alkyl group having 2 to 40 carbon atoms, and morepreferably an alkyl group having 2 to 18 carbon atoms. In theaforementioned aspect, coating film formability is more excellent, andcarrier mobility of the obtained organic semiconductor film is moreexcellent.

The compound represented by Formula 1 is preferably a compound having aline symmetric axis. In the aforementioned aspect, coating filmformability is more excellent, crystal sizes of obtained organicsemiconductor crystals are larger, and carrier mobility of the obtainedorganic semiconductor film is more excellent.

The compound represented by Formula 1 is preferably a compoundrepresented by any one of Formulae 1-1 to 1-3 below.

In Formulae 1-1 to 1-3, p and q each independently represent 1 or 2, Z'seach independently represent a hydrogen atom or a halogen atom, le andR² each independently represent a group represented by Formula W above.

Z in Formula 1-1 to Formula 1-3 and a group represented by Formula W arethe same as Z in Formula 1 and the group represented by Formula W, andpreferable aspects thereof are also the same.

p and q in Formulae 1-1 to 1-3 preferably are 1.

R¹ and R² in Formulae 1-1 to 1-3 are preferably the same group.

R¹ and R² in Formulae 1-1 to 1-3 each independently and preferablyrepresent an alkyl group.

The number of carbon atoms of R¹ in Formulae 1-1 to 1-3 is preferably 2to 40 and more preferably 2 to 18.

The number of carbon atoms of R² in Formulae 1-1 to 1-3 is preferably 2to 40 and more preferably 2 to 18.

The compound represented by Formula 1 is more preferably a compoundrepresented by any one of Formulae 1-4 to 1-6 below.

In Formulae 1-4 to 1-6, R¹ and R² each independently represent a grouprepresented by Formula W above.

The group represented by Formula W in Formulae 1-4 to 1-6 is the same asthe group represented by Formula W in Formula 1 and preferable aspectsthereof are also the same.

R¹ and R² in Formulae 1-4 to 1-6 are preferably the same group.

R¹ and R² in Formulae 1-4 to 1-6 each independently represent andpreferably an alkyl group.

The number of carbon atoms of R¹ in Formulae 1-4 to 1-6 is preferably 2to 40 and more preferably 2 to 18.

The number of carbon atoms of R² in Formulae 1-4 to 1-6 is preferably 2to 40 and more preferably 2 to 18.

Specific examples of the compound represented by Formula 1 includecompounds provided below. However, it is obvious that the presentinvention is not limited thereto. * represents a bonding position. Xa,X, Z, R₁₁, R₁₂, R₂₁, and R₂₂ in the respective tables represent Xa, X,Z, R₁₁, R₁₂, R₂₁, and R₂₂ in the compound represented by any one ofFormulae A to F.

TABLE 1 Xa X Z R₁₁ R₁₂ R₂₁ R₂₂ Compounds 1A to 1F S S H C₅H₁₁—* HC₅H₁₁—* H Compounds 2A to 2F S S H C₆H₁₃—* H C₆H₁₃—* H Compounds 3A to3F S S H C₇H₁₅—* H C₇H₁₅—* H Compounds 4A to 4F S S H C₈H₁₇—* H C₈H₁₇—*H Compounds 5A to 5F S S H C₉H₁₉—* H C₉H₁₉—* H Compounds 6A to 6F S S HC₁₀H₂₁—* H C₁₀H₂₁—* H Compounds 7A to 7F S S H C₁₁H₂₃—* H C₁₁H₂₃—* HCompounds 8A to 8F S S H C₁₂H₂₅—* H C₁₂H₂₅—* H Compounds 9A to 9F S S HC₁₃H₂₇—* H C₁₃H₂₇—* H Compounds 10A to 10F S S H C₁₄H₂₉—* H C₁₄H₂₉—* HCompounds 11A to 11F S S H C₁₅H₃₁—* H C₁₅H₃₁—* H Compounds 12A to 12F SS H C₁₆H₃₃—* H C₁₆H₃₃—* H Compounds 13A to 13F S S H C₁₇H₃₅—* H C₁₇H₃₅—*H Compounds 14A to 14F S S H C₁₈H₃₇—* H C₁₈H₃₇—* H Compounds 15A to 15FS S H p-C₅H₁₁—Ph—* H p-C₅H₁₁—Ph—* H Compounds 16A to 16F S S Hp-C₆H₁₃—Ph—* H p-C₆H₁₃—Ph—* H Compounds 17A to 17F S S H p-C₇H₁₅—Ph—* Hp-C₇H₁₅—Ph—* H Compounds 18A to 18F S S H p-C₈H₁₇—Ph—* H p-C₈H₁₇—Ph—* HCompounds 19A to 19F S S H p-C₉H₁₉—Ph—* H p-C₉H₁₉—Ph—* H Compounds 20Ato 20F S S H p-C₁₀H₂₁—Ph—* H p-C₁₀H₂₁—Ph—* H Compounds 21A to 21F S S Hp-C₁₁H₂₃—Ph—* H p-C₁₁H₂₃—Ph—* H Compounds 22A to 22F S S H p-C₁₂H₂₅—Ph—*H p-C₁₂H₂₅—Ph—* H Compounds 23A to 23F S S H p-C₁₃H₂₇—Ph—* Hp-C₁₃H₂₇—Ph—* H Compounds 24A to 24F S S H p-C₁₄H₂₉—Ph—* H p-C₁₄H₂₉—Ph—*H Compounds 25A to 25F S S H p-C₁₅H₃₁—Ph—* H p-C₁₅H₃₁—Ph—* H Compounds26A to 26F S S H p-C₁₆H₃₃—Ph—* H p-C₁₆H₃₃—Ph—* H Compounds 27A to 27F SS H p-C₁₇H₃₅—Ph—* H p-C₁₇H₃₅—Ph—* H Compounds 28A to 28F S S Hp-C₁₈H₃₇—Ph—* H p-C₁₈H₃₇—Ph—* H Compounds 29A to 29F S S H X1 H X1 HCompounds 30A to 30F S S H X2 H X2 H Compounds 31A to 31F S S H X3 H X3H Compounds 32A to 32F S S H X4 H X4 H Compounds 33A to 33F S S H X5 HX5 H Compounds 34A to 34F S S H X6 H X6 H Compounds 35A to 35F S S H X7H X7 H Compounds 36A to 36F S S H X8 H X8 H Compounds 37A to 37F S S HX9 H X9 H Compounds 38A to 38F S S H X10 H X10 H Compounds 39A to 39F SS H X11 H X11 H Compounds 40A to 40F S S H X12 H X12 H Compounds 41A to41F S S H X13 H X13 H Compounds 42A to 42F S S H X14 H X14 H Compounds43A to 43F S S F C₅H₁₁—* H C₅H₁₁—* H Compounds 44A to 44F S S F C₆H₁₃—*H C₆H₁₃—* H Compounds 45A to 45F S S F C₇H₁₅—* H C₇H₁₅—* H Compounds 46Ato 46F S S F C₈H₁₇—* H C₈H₁₇—* H Compounds 47A to 47F S S F C₉H₁₉—* HC₉H₁₉—* H Compounds 48A to 48F S S F C₁₀H₂₁—* H C₁₀H₂₁—* H Compounds 49Ato 49F S S F C₁₁H₂₃—* H C₁₁H₂₃—* H Compounds 50A to 50F S S F C₁₂H₂₅—* HC₁₂H₂₅—* H Compounds 51A to 51F S S F C₁₃H₂₇—* H C₁₃H₂₇—* H Compounds52A to 52F S S F C₁₄H₂₉—* H C₁₄H₂₉—* H Compounds 53A to 53F S S FC₁₅H₃₁—* H C₁₅H₃₁—* H Compounds 54A to 54F S S F C₁₆H₃₃—* H C₁₆H₃₃—* HCompounds 55A to 55F S S F C₁₇H₃₅—* H C₁₇H₃₅—* H Compounds 56A to 56F SS F C₁₈H₃₇—* H C₁₈H₃₇—* H Compounds 57A to 57F S S F p-C₅H₁₁—Ph—* Hp-C₅H₁₁—Ph—* H Compounds 58A to 58F S S F p-C₆H₁₃—Ph—* H p-C₆H₁₃—Ph—* HCompounds 59A to 59F S S F p-C₇H₁₅—Ph—* H p-C₇H₁₅—Ph—* H Compounds 60Ato 60F S S F p-C₈H₁₇—Ph—* H p-C₈H₁₇—Ph—* H Compounds 61A to 61F S S Fp-C₉H₁₉—Ph—* H p-C₉H₁₉—Ph—* H Compounds 62A to 62F S S F p-C₁₀H₂₁—Ph—* Hp-C₁₀H₂₁—Ph—* H Compounds 63A to 63F S S F p-C₁₁H₂₃—Ph—* H p-C₁₁H₂₃—Ph—*H Compounds 64A to 64F S S F p-C₁₂H₂₅—Ph—* H p-C₁₂H₂₅—Ph—* H Compounds65A to 65F S S F p-C₁₃H₂₇—Ph—* H p-C₁₃H₂₇—Ph—* H Compounds 66A to 66F SS F p-C₁₄H₂₉—Ph—* H p-C₁₄H₂₉—Ph—* H Compounds 67A to 67F S S Fp-C₁₅H₃₁—Ph—* H p-C₁₅H₃₁—Ph—* H Compounds 68A to 68F S S F p-C₁₆H₃₃—Ph—*H p-C₁₆H₃₃—Ph—* H Compounds 69A to 69F S S F p-C₁₇H₃₅—Ph—* Hp-C₁₇H₃₅—Ph—* H Compounds 70A to 70F S S F p-C₁₈H₃₇—Ph—* H p-C₁₈H₃₇—Ph—*H Compounds 71A to 71F S S F X1 H X1 H Compounds 72A to 72F S S F X2 HX2 H Compounds 73A to 73F S S F X3 H X3 H Compounds 74A to 74F S S F X4H X4 H Compounds 75A to 75F S S F X5 H X5 H Compounds 76A to 76F S S FX6 H X6 H Compounds 77A to 77F S S F X7 H X7 H Compounds 78A to 78F S SF X8 H X8 H Compounds 79A to 79F S S F X9 H X9 H Compounds 80A to 80F SS F X10 H X10 H Compounds 81A to 81F S S F X11 H X11 H Compounds 82A to82F S S F X12 H X12 H Compounds 83A to 83F S S F X13 H X13 H Compounds84A to 84F S S F X14 H X14 H

TABLE 2 Xa X Z R₁₁ R₁₂ R₂₁ R₂₂ Compounds 85A to 85F S S H H C₅H₁₁—* HC₅H₁₁—* Compounds 86A to 86F S S H H C₆H₁₃—* H C₆H₁₃—* Compounds 87A to87F S S H H C₇H₁₅—* H C₇H₁₅—* Compounds 88A to 88F S S H H C₈H₁₇—* HC₈H₁₇—* Compounds 89A to 89F S S H H C₉H₁₉—* H C₉H₁₉—* Compounds 90A to90F S S H H C₁₀H₂₁—* H C₁₀H₂₁—* Compounds 91A to 91F S S H H C₁₁H₂₃—* HC₁₁H₂₃—* Compounds 92A to 92F S S H H C₁₂H₂₅—* H C₁₂H₂₅—* Compounds 93Ato 93F S S H H C₁₃H₂₇—* H C₁₃H₂₇—* Compounds 94A to 94F S S H H C₁₄H₂₉—*H C₁₄H₂₉—* Compounds 95A to 95F S S H H C₁₅H₃₁—* H C₁₅H₃₁—* Compounds96A to 96F S S H H C₁₆H₃₃—* H C₁₆H₃₃—* Compounds 97A to 97F S S H HC₁₇H₃₅—* H C₁₇H₃₅—* Compounds 98A to 98F S S H H C₁₈H₃₇—* H C₁₈H₃₇—*Compounds 99A to 99F S S H H p-C₅H₁₁—Ph—* H p-C₅H₁₁—Ph—* Compounds 100Ato 100F S S H H p-C₆H₁₃—Ph—* H p-C₆H₁₃—Ph—* Compounds 101A to 101F S S HH p-C₇H₁₅—Ph—* H p-C₇H₁₅—Ph—* Compounds 102A to 102F S S H Hp-C₈H₁₇—Ph—* H p-C₈H₁₇—Ph—* Compounds 103A to 103F S S H H p-C₉H₁₉—Ph—*H p-C₉H₁₉—Ph—* Compounds 104A to 104F S S H H p-C₁₀H₂₁—Ph—* Hp-C₁₀H₂₁—Ph—* Compounds 105A to 105F S S H H p-C₁₁H₂₃—Ph—* Hp-C₁₁H₂₃—Ph—* Compounds 106A to 106F S S H H p-C₁₂H₂₅—Ph—* Hp-C₁₂H₂₅—Ph—* Compounds 107A to 107F S S H H p-C₁₃H₂₇—Ph—* Hp-C₁₃H₂₇—Ph—* Compounds 108A to 108F S S H H p-C₁₄H₂₉—Ph—* Hp-C₁₄H₂₉—Ph—* Compounds 109A to 109F S S H H p-C₁₅H₃₁—Ph—* Hp-C₁₅H₃₁—Ph—* Compounds 110A to 110F S S H H p-C₁₆H₃₃—Ph—* Hp-C₁₆H₃₃—Ph—* Compounds 111A to 111F S S H H p-C₁₇H₃₅—Ph—* Hp-C₁₇H₃₅—Ph—* Compounds 112A to 112F S S H H p-C₁₈H₃₇—Ph—* Hp-C₁₈H₃₇—Ph—* Compounds 113A to 113F S S H H X1 H X1 Compounds 114A to114F S S H H X2 H X2 Compounds 115A to 115F S S H H X3 H X3 Compounds116A to 116F S S H H X4 H X4 Compounds 117A to 117F S S H H X5 H X5Compounds 118A to 118F S S H H X6 H X6 Compounds 119A to 119F S S H H X7H X7 Compounds 120A to 120F S S H H X8 H X8 Compounds 121A to 121F S S HH X9 H X9 Compounds 122A to 122F S S H H X10 H X10 Compounds 123A to123F S S H H X11 H X11 Compounds 124A to 124F S S H H X12 H X12Compounds 125A to 125F S S H H X13 H X13 Compounds 126A to 126F S S H HX14 H X14 Compounds 127A to 127F S S H H H C₅H₁₁—* H Compounds 128A to128F S S H H H C₆H₁₃—* H Compounds 129A to 129F S S H H H C₇H₁₅—* HCompounds 130A to 130F S S H H H C₈H₁₇—* H Compounds 131A to 131F S S HH H C₉H₁₉—* H Compounds 132A to 132F S S H H H C₁₀H₂₁—* H Compounds 133Ato 133F S S H H H C₁₁H₂₃—* H Compounds 134A to 134F S S H H H C₁₂H₂₅—* HCompounds 135A to 135F S S H H H C₁₃H₂₇—* H Compounds 136A to 136F S S HH H C₁₄H₂₉—* H Compounds 137A to 137F S S H H H C₁₅H₃₁—* H Compounds138A to 138F S S H H H C₁₆H₃₃—* H Compounds 139A to 139F S S H H HC₁₇H₃₅—* H Compounds 140A to 140F S S H H H C₁₈H₃₇—* H Compounds 141A to141F S S H H H H C₅H₁₁—* Compounds 142A to 142F S S H H H H C₆H₁₃—*Compounds 143A to 143F S S H H H H C₇H₁₅—* Compounds 144A to 144F S S HH H H C₈H₁₇—* Compounds 145A to 145F S S H H H H C₉H₁₉—* Compounds 146Ato 146F S S H H H H C₁₀H₂₁—* Compounds 147A to 147F S S H H H H C₁₁H₂₃—*Compounds 148A to 148F S S H H H H C₁₂H₂₅—* Compounds 149A to 149F S S HH H H C₁₃H₂₇—* Compounds 150A to 150F S S H H H H C₁₄H₂₉—* Compounds151A to 151F S S H H H H C₁₅H₃₁—* Compounds 152A to 152F S S H H H HC₁₆H₃₃—* Compounds 153A to 153F S S H H H H C₁₇H₃₅—* Compounds 154A to154F S S H H H H C₁₈H₃₇—* Compounds 155A to 155F S S H H H p-C₅H₁₁—Ph—*H Compounds 156A to 156F S S H H H p-C₆H₁₃—Ph—* H Compounds 157A to 157FS S H H H p-C₇H₁₅—Ph—* H Compounds 158A to 158F S S H H H p-C₈H₁₇—Ph—* HCompounds 159A to 159F S S H H H p-C₉H₁₉—Ph—* H Compounds 160A to 160F SS H H H p-C₁₀H₂₁—Ph—* H Compounds 161A to 161F S S H H H p-C₁₁H₂₃—Ph—* HCompounds 162A to 162F S S H H H p-C₁₂H₂₅—Ph—* H Compounds 163A to 163FS S H H H p-C₁₃H₂₇—Ph—* H Compounds 164A to 164F S S H H H p-C₁₄H₂₉—Ph—*H Compounds 165A to 165F S S H H H p-C₁₅H₃₁—Ph—* H Compounds 166A to166F S S H H H p-C₁₆H₃₃—Ph—* H Compounds 167A to 167F S S H H Hp-C₁₇H₃₅—Ph—* H Compounds 168A to 168F S S H H H p-C₁₆H₃₇—Ph—* H

TABLE 3 Xa X Z R₁₁ R₁₂ R₂₁ R₂₂ Compounds 169A to 169F S S H H H Hp-C₅H₁₁—Ph—* Compounds 170A to 170F S S H H H H p-C₆H₁₃—Ph—* Compounds171A to 171F S S H H H H p-C₇H₁₅—Ph—* Compounds 172A to 172F S S H H H Hp-C₈H₁₇—Ph—* Compounds 173A to 173F S S H H H H p-C₉H₁₉—Ph—* Compounds174A to 174F S S H H H H p-C₁₀H₂₁—Ph—* Compounds 175A to 175F S S H H HH p-C₁₁H₂₃—Ph—* Compounds 176A to 176F S S H H H H p-C₁₂H₂₅—Ph—*Compounds 177A to 177F S S H H H H p-C₁₃H₂₇—Ph—* Compounds 178A to 178FS S H H H H p-C₁₄H₂₉—Ph—* Compounds 179A to 179F S S H H H Hp-C₁₅H₃₁—Ph—* Compounds 180A to 180F S S H H H H p-C₁₆H₃₃—Ph—* Compounds181A to 181F S S H H H H p-C₁₇H₃₅—Ph—* Compounds 182A to 182F S S H H HH p-C₁₈H₃₇—Ph—* Compounds 183A to 183F S S H H H X1 H Compounds 184A to184F S S H H H X2 H Compounds 185A to 185F S S H H H X3 H Compounds 186Ato 186F S S H H H X4 H Compounds 187A to 187F S S H H H X5 H Compounds188A to 188F S S H H H X6 H Compounds 189A to 189F S S H H H X7 HCompounds 190A to 190F S S H H H X8 H Compounds 191A to 191F S S H H HX9 H Compounds 192A to 192F S S H H H X10 H Compounds 193A to 193F S S HH H X11 H Compounds 194A to 194F S S H H H X12 H Compounds 195A to 195FS S H H H X13 H Compounds 196A to 196F S S H H H H X1 Compounds 197A to197F S S H H H H X2 Compounds 198A to 198F S S H H H H X3 Compounds 199Ato 199F S S H H H H X4 Compounds 200A to 200F S S H H H H X5 Compounds201A to 201F S S H H H H X6 Compounds 202A to 202F S S H H H H X7Compounds 203A to 203F S S H H H H X8 Compounds 204A to 204F S S H H H HX9 Compounds 205A to 205F S S H H H H X10 Compounds 206A to 206F S S H HH H X11 Compounds 207A to 207F S S H H H H X12 Compounds 208A to 208F SS H H H H X13

TABLE 4 Xa X Z R₁₁ R₁₂ R₂₁ R₂₂ Compounds 209A to 209F S S H C₁₂H₂₅—* Hp-C₅H₁₁—Ph—* H Compounds 210A to 210F S S H C₁₂H₂₅—* H p-C₆H₁₃—Ph—* HCompounds 211A to 211F S S H C₁₂H₂₅—* H p-C₇H₁₅—Ph—* H Compounds 212A to212F S S H C₁₂H₂₅—* H p-C₈H₁₇—Ph—* H Compounds 213A to 213F S S HC₁₂H₂₅—* H p-C₉H₁₉—Ph—* H Compounds 214A to 214F S S H C₁₂H₂₅—* Hp-C₁₀H₂₁—Ph—* H Compounds 215A to 215F S S H C₁₂H₂₅—* H p-C₁₁H₂₃—Ph—* HCompounds 216A to 216F S S H C₁₂H₂₅—* H p-C₁₂H₂₅—Ph—* H Compounds 217Ato 217F S S H C₁₂H₂₅—* H p-C₁₃H₂₇—Ph—* H Compounds 218A to 218F S S HC₁₂H₂₅—* H p-C₁₄H₂₉—Ph—* H Compounds 219A to 219F S S H C₁₂H₂₅—* Hp-C₁₅H₃₁—Ph—* H Compounds 220A to 220F S S H C₁₂H₂₅—* H p-C₁₆H₃₃—Ph—* HCompounds 221A to 221F S S H C₁₂H₂₅—* H p-C₁₇H₃₅—Ph—* H Compounds 222Ato 222F S S H C₁₂H₂₅—* H p-C₁₈H₃₇—Ph—* H Compounds 223A to 223F S S HC₁₂H₂₅—* H X1 H Compounds 224A to 224F S S H C₁₂H₂₅—* H X2 H Compounds225A to 225F S S H C₁₂H₂₅—* H X3 H Compounds 226A to 226F S S H C₁₂H₂₅—*H X4 H Compounds 227A to 227F S S H C₁₂H₂₅—* H X5 H Compounds 228A to228F S S H C₁₂H₂₅—* H X6 H Compounds 229A to 229F S S H C₁₂H₂₅—* H X7 HCompounds 230A to 230F S S H C₁₂H₂₅—* H X8 H Compounds 231A to 231F S SH C₁₂H₂₅—* H X9 H Compounds 232A to 232F S S H C₁₂H₂₅—* H X10 HCompounds 233A to 233F S S H C₁₂H₂₅—* H X11 H Compounds 234A to 234F S SH C₁₂H₂₅—* H X12 H Compounds 235A to 235F S S H C₁₂H₂₅—* H X13 HCompounds 236A to 236F S S H C₁₂H₂₅—* H X14 H Compounds 237A to 237F S SH C₁₂H₂₅—* H H C₅H₁₁—* Compounds 238A to 238F S S H C₁₂H₂₅—* H H C₆H₁₃—*Compounds 239A to 239F S S H C₁₂H₂₅—* H H C₇H₁₅—* Compounds 240A to 240FS S H C₁₂H₂₅—* H H C₈H₁₇—* Compounds 241A to 241F S S H C₁₂H₂₅—* H HC₉H₁₉—* Compounds 242A to 242F S S H C₁₂H₂₅—* H H C₁₀H₂₁—* Compounds243A to 243F S S H C₁₂H₂₅—* H H C₁₁H₂₃—* Compounds 244A to 244F S S HC₁₂H₂₅—* H H C₁₂H₂₅—* Compounds 245A to 245F S S H C₁₂H₂₅—* H H C₁₃H₂₇—*Compounds 246A to 246F S S H C₁₂H₂₅—* H H C₁₄H₂₉—* Compounds 247A to247F S S H C₁₂H₂₅—* H H C₁₅H₃₁—* Compounds 248A to 248F S S H C₁₂H₂₅—* HH C₁₆H₃₃—* Compounds 249A to 249F S S H C₁₂H₂₅—* H H C₁₇H₃₅—* Compounds250A to 250F S S H C₁₂H₂₅—* H H C₁₈H₃₇—* Compounds 251A to 251F S S HC₁₂H₂₅—* H H p-C₅H₁₁—Ph—* Compounds 252A to 252F S S H C₁₂H₂₅—* H Hp-C₆H₁₃—Ph—* Compounds 253A to 253F S S H C₁₂H₂₅—* H H p-C₇H₁₅—Ph—*Compounds 254A to 254F S S H C₁₂H₂₅—* H H p-C₈H₁₇—Ph—* Compounds 255A to255F S S H C₁₂H₂₅—* H H p-C₉H₁₉—Ph—* Compounds 256A to 256F S S HC₁₂H₂₅—* H H p-C₁₀H₂₁—Ph—* Compounds 257A to 257F S S H C₁₂H₂₅—* H Hp-C₁₁H₂₃—Ph—* Compounds 258A to 258F S S H C₁₂H₂₅—* H H p-C₁₂H₂₅—Ph—*Compounds 259A to 259F S S H C₁₂H₂₅—* H H p-C₁₃H₂₇—Ph—* Compounds 260Ato 260F S S H C₁₂H₂₅—* H H p-C₁₄H₂₉—Ph—* Compounds 261A to 261F S S HC₁₂H₂₅—* H H p-C₁₅H₃₁—Ph—* Compounds 262A to 262F S S H C₁₂H₂₅—* H Hp-C₁₆H₃₃—Ph—* Compounds 263A to 263F S S H C₁₂H₂₅—* H H p-C₁₇H₃₅—Ph—*Compounds 264A to 264F S S H C₁₂H₂₅—* H H p-C₁₈H₃₇—Ph—* Compounds 265Ato 265F S S H H C₁₂H₂₅—* H p-C₅H₁₁—Ph—* Compounds 266A to 266F S S H HC₁₂H₂₅—* H p-C₆H₁₃—Ph—* Compounds 267A to 267F S S H H C₁₂H₂₅—* Hp-C₇H₁₅—Ph—* Compounds 268A to 268F S S H H C₁₂H₂₅—* H p-C₈H₁₇—Ph—*Compounds 269A to 269F S S H H C₁₂H₂₅—* H p-C₉H₁₉—Ph—* Compounds 270A to270F S S H H C₁₂H₂₅—* H p-C₁₀H₂₁—Ph—* Compounds 271A to 271F S S H HC₁₂H₂₅—* H p-C₁₁H₂₃—Ph—* Compounds 272A to 272F S S H H C₁₂H₂₅—* Hp-C₁₂H₂₅—Ph—* Compounds 273A to 273F S S H H C₁₂H₂₅—* H p-C₁₃H₂₇—Ph—*Compounds 274A to 274F S S H H C₁₂H₂₅—* H p-C₁₄H₂₉—Ph—* Compounds 275Ato 275F S S H H C₁₂H₂₅—* H p-C₁₅H₃₁—Ph—* Compounds 276A to 276F S S H HC₁₂H₂₅—* H p-C₁₆H₃₃—Ph—* Compounds 277A to 277F S S H H C₁₂H₂₅—* Hp-C₁₇H₃₅—Ph—* Compounds 278A to 278F S S H H C₁₂H₂₅—* H p-C₁₈H₃₇—Ph—*

TABLE 5 Xa X Z R₁₁ R₁₂ R₂₁ R₂₂ Compounds 279A to 279F S S H

H

H Compounds 280A to 280F S S H

H

H Compounds 281A to 281F S S H

H

H Compounds 282A to 282F S S H

H

H Compounds 283A to 283F S S H

H

H Compounds 284A to 284F S S H

H

H Compounds 285A to 285F S S H

H

H Compounds 286A to 286F S S H

H

H Compounds 287A to 287F S S H

H

H Compounds 288A to 288F S S H

H

H Compounds 289A to 289F S S H

H

H Compounds 290A to 290F S S H

H

H Compounds 291A to 291F S S H

H

H Compounds 292A to 292F S S H

H

H Compounds 293A to 293F S S H

H

H Compounds 294A to 294F S S H

H

H Compounds 295A to 295F S S H

H

H Compounds 296A to 296F S S H

H

H Compounds 297A to 297F S S H

H

H Compounds 298A to 298F S S H

H

H Compounds 299A to 299F S S H

H

H

TABLE 6 Xa X Z R₁₁ R₁₂ R₂₁ R₂₂ Compounds 300A to 300F S S H

H

H Compounds 301A to 301F S S H

H

H Compounds 302A to 302F S S H

H

H Compounds 303A to 303F S S H

H

H Compounds 304A to 304F S S H

H

H Compounds 305A to 305F S S H

H

H Compounds 306A to 306F S S H

H

H Compounds 307A to 307F S S H

H

H Compounds 308A to 308F S S H

H

H Compounds 309A to 309F S S H

H

H Compounds 310A to 310F S S H

H

H Compounds 311A to 311F S S H

H

H Compounds 312A to 312F S S H

H

H Compounds 313A to 313F S S H

H

H Compounds 314A to 314F S S H

H

H Compounds 315A to 315F S S H

H

H Compounds 316A to 316F S S H

H

H Compounds 317A to 317F S S H

H

H Compounds 318A to 318F S S H

H

H Compounds 319A to 319F S S H

H

H

TABLE 7 Xa X Z R₁₁ R₁₂ R₂₁ R₂₂ Compounds 320A to 320F O O H p-C₅H₁₁—* Hp-C₅H₁₁—* H Compounds 321A to 321F O O H p-C₆H₁₃—* H p-C₆H₁₃—* HCompounds 322A to 322F O O H p-C₇H₁₅—* H p-C₇H₁₅—* H Compounds 323A to323F O O H p-C₈H₁₇—* H p-C₈H₁₇—* H Compounds 324A to 324F O O Hp-C₉H₁₉—* H p-C₉H₁₉—* H Compounds 325A to 325F O O H p-C₁₀H₂₁—* Hp-C₁₀H₂₁—* H Compounds 326A to 326F O O H p-C₁₁H₂₃—* H p-C₁₁H₂₃—* HCompounds 327A to 327F O O H p-C₁₂H₂₅—* H p-C₁₂H₂₅—* H Compounds 328A to328F O O H p-C₁₃H₂₇—* H p-C₁₃H₂₇—* H Compounds 329A to 329F O O Hp-C₁₄H₂₉—* H p-C₁₄H₂₉—* H Compounds 330A to 330F O O H p-C₁₅H₃₁—* Hp-C₁₅H₃₁—* H Compounds 331A to 331F O O H p-C₁₆H₃₃—* H p-C₁₆H₃₃—* HCompounds 332A to 332F O O H p-C₁₇H₃₅—* H p-C₁₇H₃₅—* H Compounds 333A to333F O O H p-C₁₈H₃₇—* H p-C₁₈H₃₇—* H Compounds 334A to 334F O O Hp-C₅H₁₁—Ph—* H p-C₅H₁₁—Ph—* H Compounds 335A to 335F O O H p-C₆H₁₃—Ph—*H p-C₆H₁₃—Ph—* H Compounds 336A to 336F O O H p-C₇H₁₅—Ph—* Hp-C₇H₁₅—Ph—* H Compounds 337A to 337F O O H p-C₈H₁₇—Ph—* H p-C₈H₁₇—Ph—*H Compounds 338A to 338F O O H p-C₉H₁₉—Ph—* H p-C₉H₁₉—Ph—* H Compounds339A to 339F O O H p-C₁₀H₂₁—Ph—* H p-C₁₀H₂₁—Ph—* H Compounds 340A to340F O O H p-C₁₁H₂₃—Ph—* H p-C₁₁H₂₃—Ph—* H Compounds 341A to 341F O O Hp-C₁₂H₂₅—Ph—* H p-C₁₂H₂₅—Ph—* H Compounds 342A to 342F O O Hp-C₁₃H₂₇—Ph—* H p-C₁₃H₂₇—Ph—* H Compounds 343A to 343F O O Hp-C₁₄H₂₉—Ph—* H p-C₁₄H₂₉—Ph—* H Compounds 344A to 344F O O Hp-C₁₅H₃₁—Ph—* H p-C₁₅H₃₁—Ph—* H Compounds 345A to 345F O O Hp-C₁₆H₃₃—Ph—* H p-C₁₆H₃₃—Ph—* H Compounds 346A to 346F O O Hp-C₁₇H₃₅—Ph—* H p-C₁₇H₃₅—Ph—* H Compounds 347A to 347F O O Hp-C₁₈H₃₇—Ph—* H p-C₁₈H₃₇—Ph—* H Compounds 348A to 348F O O H X1 H X1 HCompounds 349A to 349F O O H X2 H X2 H Compounds 350A to 350F O O H X3 HX3 H Compounds 351A to 351F O O H X4 H X4 H Compounds 352A to 352F O O HX5 H X5 H Compounds 353A to 353F O O H X6 H X6 H Compounds 354A to 354FO O H X7 H X7 H Compounds 355A to 355F O O H X8 H X8 H Compounds 356A to356F O O H X9 H X9 H Compounds 357A to 357F O O H X10 H X10 H Compounds358A to 358F O O H X11 H X11 H Compounds 359A to 339F O O H X12 H X12 HCompounds 360A to 360F O O H X13 H X13 H Compounds 361A to 361F O O HX14 H X14 H Compounds 362A to 362F S S H C₄H₉OC₄H₈—* H C₄H₉OC₄H₈—* HCompounds 363A to 363F S S H C₂H₅OC₂H₄—* H C₂H₅OC₂H₄—* H Compounds 364Ato 364F S S H C₆H₁₃OC₄H₈—* H C₆H₁₃OC₄H₈—* H Compounds 365A to 365F S S HC₂H₅OC₄H₈—* H C₂H₅OC₄H₈—* H Compounds 366A to 366F S S H CH₃OC₃H₆—* HCH₃OC₃H₆—* H Compounds 367A to 367F S S H PhC₃H₆—* H PhC₃H₆—* HCompounds 368A to 368F S S H PhOC₃H₆—* H PhOC₃H₆—* H

TABLE 8 Xa X Z R₁₁ R₁₂ R₂₁ R₂₂ Compounds 369A to 369C S S H

H

H Compounds 370A to 370C S S H

H

H Compounds 371A to 371C S S H

H

H Compounds 372A to 372C S S H

H

H Compounds 373A to 373C S S H

H

H Compounds 374A to 374C S S H 3,7-Dimethyloctyl H C,.7-Dimethyloctyl HCompounds 375A to 375C S S H 3,7-Dimethyloctyl H H H Compounds 376A to376C S S H 2-Ethylhexyl H 2-Ethylhexyl H Compounds 377A to 377C S S H

H

H Compounds 378A to 378C S S H

H

H Compounds 379A to 379C S S H

H

H Compounds 380A to 380C S S H

H H H Compounds 381A to 381C S S H

H

H Compounds 382A to 382C S S H C₆H₁₁—* H

H Compounds 383A to 383C S S H

H

H Compounds 384A to 384C S S H

H

H Compounds 385A to 385C S S H

H

H Compounds 386A to 386C S S H

H

H Compounds 387A to 387C S S H

H

H Compounds 388A to 388C S S H

H H H Compounds 389A to 389C S S H

H

H Compounds 390A to 390C S S H

H

H Compounds 391A to 391C S S H

H

H Compounds 392A to 392C S S H

H

H

TABLE 9 Xa X Z R₁₁ R₁₂ R₂₁ R₂₂ Compounds 393D to 393F S S H p-C₅H₁₁—* HH H Compounds 394D to 394F S S H p-C₆H₁₃—* H H H Compounds 395D to 395FS S H p-C₇H₁₅—* H H H Compounds 396D to 396F S S H p-C₈H₁₇—* H H HCompounds 397D to 397F S S H p-C₉H₁₉—* H H H Compounds 398D to 398F S SH p-C₁₀H₂₁—* H H H Compounds 399D to 399F S S H p-C₁₁H₂₃—* H H HCompounds 400D to 400F S S H p-C₁₂H₂₅—* H H H Compounds 401D to 401F S SH p-C₁₃H₂₇—* H H H Compounds 402D to 402F S S H p-C₁₄H₂₉—* H H HCompounds 403D to 403F S S H p-C₁₅H₃₁—* H H H Compounds 404D to 404F S SH p-C₁₆H₃₃—* H H H Compounds 405D to 405F S S H p-C₁₇H₃₅—* H H HCompounds 406D to 406F S S H p-C₁₈H₃₇—* H H H Compounds 407D to 407F S SH H p-C₅H₁₁—* H H Compounds 408D to 408F S S H H p-C₆H₁₃—* H H Compounds409D to 409F S S H H p-C₇H₁₅—* H H Compounds 410D to 410F S S H Hp-C₈H₁₇—* H H Compounds 411D to 411F S S H H p-C₉H₁₉—* H H Compounds412D to 412F S S H H p-C₁₀H₂₁—* H H Compounds 413D to 413F S S H Hp-C₁₁H₂₃—* H H Compounds 414D to 414F S S H H p-C₁₂H₂₅—* H H Compounds415D to 415F S S H H p-C₁₃H₂₇—* H H Compounds 416D to 416F S S H Hp-C₁₄H₂₉—* H H Compounds 417D to 417F S S H H p-C₁₅H₃₁—* H H Compounds418D to 418F S S H H p-C₁₆H₃₃—* H H Compounds 419D to 419F S S H Hp-C₁₇H₃₅—* H H Compounds 420D to 420F S S H H p-C₁₈H₃₇—* H H Compounds421D to 421F S S H p-C₅H₁₁—Ph—* H H H Compounds 422D to 422F S S Hp-C₆H₁₃—Ph—* H H H Compounds 423D to 423F S S H p-C₇H₁₅—Ph—* H H HCompounds 424D to 424F S S H p-C₈H₁₇—Ph—* H H H Compounds 425D to 425F SS H p-C₉H₁₉—Ph—* H H H Compounds 426D to 426F S S H p-C₁₀H₂₁—Ph—* H H HCompounds 427D to 427F S S H p-C₁₁H₂₃—Ph—* H H H Compounds 428D to 428FS S H p-C₁₂H₂₅—Ph—* H H H Compounds 429D to 429F S S H p-C₁₃H₂₇—Ph—* H HH Compounds 430D to 430F S S H p-C₁₄H₂₉—Ph—* H H H Compounds 431D to431F S S H p-C₁₅H₃₁—Ph—* H H H Compounds 432D to 432F S S Hp-C₁₆H₃₃—Ph—* H H H Compounds 433D to 433F S S H p-C₁₇H₃₅—Ph—* H H HCompounds 434D to 434F S S H p-C₁₈H₃₇—Ph—* H H H Compounds 435D to 435FS S H H p-C₅H₁₁—Ph—* H H Compounds 436D to 436F S S H H p-C₆H₁₃—Ph—* H HCompounds 437D to 437F S S H H p-C₇H₁₅—Ph—* H H Compounds 438D to 438F SS H H p-C₈H₁₇—Ph—* H H Compounds 439D to 439F S S H H p-C₉H₁₉—Ph—* H HCompounds 440D to 440F S S H H p-C₁₀H₂₁—Ph—* H H Compounds 441D to 441FS S H H p-C₁₁H₂₃—Ph—* H H Compounds 442D to 442F S S H H p-C₁₂H₂₅—Ph—* HH Compounds 443D to 443F S S H H p-C₁₃H₂₇—Ph—* H H Compounds 444D to444F S S H H p-C₁₄H₂₉—Ph—* H H Compounds 445D to 445F S S H Hp-C₁₅H₃₁—Ph—* H H Compounds 446D to 446F S S H H p-C₁₆H₃₃—Ph—* H HCompounds 447D to 447F S S H H p-C₁₇H₃₅—Ph—* H H Compounds 448D to 448FS S H H p-C₁₈H₃₇—Ph—* H H Compounds 449D to 449F S S H X1 H H HCompounds 450D to 450F S S H X2 H H H Compounds 451D to 451F S S H X3 HH H Compounds 452D to 452F S S H X4 H H H Compounds 453D to 453F S S HX5 H H H Compounds 454D to 454F S S H X6 H H H Compounds 455D to 455F SS H X7 H H H Compounds 456D to 456F S S H X8 H H H Compounds 457D to457F S S H X9 H H H Compounds 458D to 458F S S H X10 H H H Compounds459D to 459F S S H X11 H H H Compounds 460D to 460F S S H X12 H H HCompounds 461D to 461F S S H X13 H H H Compounds 462D to 462F S S H X14H H H Compounds 463D to 463F S S H H X1 H H Compounds 464D to 464F S S HH X2 H H Compounds 465D to 465F S S H H X3 H H Compounds 466D to 466F SS H H X4 H H Compounds 467D to 467F S S H H X5 H H Compounds 468D to468F S S H H X6 H H Compounds 469D to 469F S S H H X7 H H Compounds 470Dto 470F S S H H X8 H H Compounds 471D to 471F S S H H X9 H H Compounds472D to 472F S S H H X10 H H Compounds 473D to 473F S S H H X11 H HCompounds 474D to 474F S S H H X12 H H Compounds 475D to 475F S S H HX13 H H Compounds 476D to 476F S S H H X14 H H

TABLE 10 Xa X Z R₁₁ R₂₂ R₂₁ R₂₂ Compounds 477D to 477F S S Hp-C₅H₁₁—Ph—* H C₁₂H₂₅—* H Compounds 478D to 478F S S H p-C₆H₁₃—Ph—* HC₁₂H₂₅—* H Compounds 479D to 479F S S H p-C₇H₁₅—Ph—* H C₁₂H₂₅—* HCompounds 480D to 480F S S H p-C₈H₁₇—Ph—* H C₁₂H₂₅—* H Compounds 481D to481F S S H p-C₉H₁₉—Ph—* H C₁₂H₂₅—* H Compounds 482D to 482F S S Hp-C₁₀H₂₁—Ph—* H C₁₂H₂₅—* H Compounds 483D to 483F S S H p-C₁₁H₂₃—Ph—* HC₁₂H₂₅—* H Compounds 484D to 484F S S H p-C₁₂H₂₅—Ph—* H C₁₂H₂₅—* HCompounds 485D to 485F S S H p-C₁₃H₂₇—Ph—* H C₁₂H₂₅—* H Compounds 486Dto 486F S S H p-C₁₄H₂₉—Ph—* H C₁₂H₂₅—* H Compounds 487D to 487F S S Hp-C₁₅H₃₁—Ph—* H C₁₂H₂₅—* H Compounds 488D to 488F S S H p-C₁₆H₃₃—Ph—* HC₁₂H₂₅—* H Compounds 489D to 489F S S H p-C₁₇H₃₅—Ph—* H C₁₂H₂₅—* HCompounds 490D to 490F S S H p-C₁₈H₃₇—Ph—* H C₁₂H₂₅—* H Compounds 491Dto 491F S S H H C₁₂H₂₅—* C₅H₁₁—* H Compounds 492D to 492F S S H HC₁₂H₂₅—* C₆H₁₃—* H Compounds 493D to 493F S S H H C₁₂H₂₅—* C₇H₁₅—* HCompounds 494D to 494F S S H H C₁₂H₂₅—* C₈H₁₇—* H Compounds 495D to 495FS S H H C₁₂H₂₅—* C₉H₁₉—* H Compounds 496D to 496F S S H H C₁₂H₂₅—*C₁₀H₂₁—* H Compounds 497D to 497F S S H H C₁₂H₂₅—* C₁₁H₂₃—* H Compounds498D to 498F S S H H C₁₂H₂₅—* C₁₂H₂₅—* H Compounds 499D to 499F S S H HC₁₂H₂₅—* C₁₃H₂₇—* H Compounds 500D to 500F S S H H C₁₂H₂₅—* C₁₄H₂₉—* HCompounds 501D to 501F S S H H C₁₂H₂₅—* C₁₅H₃₁—* H Compounds 502D to502F S S H H C₁₂H₂₅—* C₁₆H₃₃—* H Compounds 503D to 503F S S H H C₁₂H₂₅—*C₁₇H₃₅—* H Compounds 504D to 504F S S H H C₁₂H₂₅—* C₁₈H₃₇—* H Compounds505D to 505F S S H H p-C₅H₁₁—Ph—* C₁₂H₂₅—* H Compounds 506D to 506F S SH H p-C₆H₁₃—Ph—* C₁₂H₂₅—* H Compounds 507D to 507F S S H H p-C₇H₁₅—Ph—*C₁₂H₂₅—* H Compounds 508D to 508F S S H H p-C₈H₁₇—Ph—* C₁₂H₂₅—* HCompounds 509D to 509F S S H H p-C₉H₁₉—Ph—* C₁₂H₂₅—* H Compounds 510D to510F S S H H p-C₁₀H₂₁—Ph—* C₁₂H₂₅—* H Compounds 511D to 511F S S H Hp-C₁₁H₂₃—Ph—* C₁₂H₂₅—* H Compounds 512D to 512F S S H H p-C₁₂H₂₅—Ph—*C₁₂H₂₅—* H Compounds 513D to 513F S S H H p-C₁₃H₂₇—Ph—* C₁₂H₂₅—* HCompounds 514D to 514F S S H H p-C₁₄H₂₉—Ph—* C₁₂H₂₅—* H Compounds 515Dto 515F S S H H p-C₁₅H₃₁—Ph—* C₁₂H₂₅—* H Compounds 516D to 516F S S H Hp-C₁₆H₃₃—Ph—* C₁₂H₂₅—* H Compounds 517D to 517F S S H H p-C₁₇H₃₅—Ph—*C₁₂H₂₅—* H Compounds 518D to 518F S S H H p-C₁₈H₃₇—Ph—* C₁₂H₂₅—* H

Abbreviations in the compounds are provided below.

Ph—: Phenyl group

—Ph—: Phenylene group

A method of synthesizing the compound represented by Formula 1 is notparticularly limited and the compound represented by Formula 1 can besynthesized with reference to the well-known methods. Examples of thesynthesization method include a method of introducing substituents (R¹and R²) by coupling reaction using a transition metal catalyst to afused polycyclic aromatic ring compound.

The compound represented by Formula 1 may be used singly or two or moretypes thereof may be used in combination.

In the semiconductor active layer of the organic semiconductor elementaccording to the present invention or an organic semiconductor filmaccording to the present invention described below, a content of thecompound represented by Formula 1 is preferably 30 to 100 mass %, morepreferably 50 to 100 mass %, and even more preferably 70 to 100 mass %.In a case where a binder polymer described below is not contained, thetotal content is preferably 90 to 100 mass % and more preferably 95 to100 mass %.

<Binder Polymer>

A semiconductor active layer of an organic semiconductor elementaccording to the present invention preferably contains a binder polymer.

The organic semiconductor element according to the present invention maybe an organic semiconductor element having the semiconductor activelayer and a layer including a binder polymer.

The types of the binder polymer are not particularly limited, andwell-known binder polymers can be used.

Examples of the binder polymer include a polystyrene resin, an acrylicresin, rubber, and a thermoplastic elastomer.

Among these, as the binder polymer, a polymer compound (a polymer havinga monomer unit having a benzene ring group) having a benzene ring ispreferable. The content of the monomer unit having a benzene ring groupis not particularly limited. However, the content is preferably 50 mol %or greater, more preferably 70 mol % or greater, and even morepreferably 90 mol % or greater with respect to the entire monomer unit.The upper limit is not particularly limited, but examples of the upperlimit include 100 mol %.

Examples of the binder polymer include polystyrene,poly(α-methylstyrene), polyvinyl cinnamate, poly(4-vinylphenyl), andpoly(4-methyl styrene).

A weight-average molecular weight of the binder polymer is notparticularly limited, but is preferably 1,000 to 2,000,000, morepreferably 3,000 to 1,000,000, and even more preferably 5,000 to600,000.

In a case where a solvent described below is used, it is preferable thatthe binder polymer exhibits solubility higher than the solubility of thecompound represented by Formula 1 in a used solvent. If the above aspectis adopted, mobility and heat resistance of the obtained organicsemiconductor are further improved.

A content of the binder polymer in the semiconductor active layer of theorganic semiconductor element of the present invention is preferably 1to 200 parts by mass, more preferably 10 to 150 parts by mass, and evenmore preferably 20 to 120 parts by mass with respect to 100 parts bymass of the content of the compound represented by Formula 1. If thecontent is within the above range, mobility and heat resistance of theobtained organic semiconductor are further improved.

<Other Components>

Other components may be included other than the compound represented byFormula 1 and the binder polymer may be included in the semiconductoractive layer according to the organic semiconductor element of thepresent invention.

As other components, known additives and the like can be used.

In the semiconductor active layer, a content of the components otherthan the compound represented by Formula 1 and the binder polymer ispreferably 10 mass % or less, more preferably 5 mass % or less, evenmore preferably 1 mass % or less, and particularly preferably 0.1 mass %or less. If the content of other components is within the above range,film formability is improved, and mobility and heat resistance of theobtained organic semiconductor are further improved.

The method of forming the semiconductor active layer according to theorganic semiconductor element of the present invention is notparticularly limited. However, a desired semiconductor active layer canbe formed by applying the organic semiconductor composition according tothe present invention described below to a source electrode, a drainelectrode, and a gate insulating film and performing a drying treatment,if necessary.

The organic semiconductor element of the present invention is preferablymanufactured using the organic semiconductor composition of the presentinvention described below.

A method of manufacturing an organic semiconductor film or an organicsemiconductor element by using the organic semiconductor composition ofthe present invention is not particularly limited, and known methods canbe adopted. Examples thereof include a method of manufacturing anorganic semiconductor film by applying the composition onto apredetermined base material and if necessary, performing a dryingtreatment.

The method of applying the composition onto a base material is notparticularly limited, and known methods can be adopted. Examples thereofinclude an ink jet printing method, a screen printing method, aflexographic printing method, a bar coating method, a spin coatingmethod, a knife coating method, a doctor blade method, and the like.Among these, an ink jet printing method, a screen printing method, and aflexographic printing method are preferable.

Preferred examples of the flexographic printing method include an aspectin which a photosensitive resin plate is used as a flexographic printingplate. By printing the composition onto a substrate according to theaspect, a pattern can be easily formed.

Among the above methods, the method of manufacturing an organicsemiconductor element of the present invention preferably includes acoating step of coating a substrate with the organic semiconductorcomposition of the present invention described below. The method ofmanufacturing an organic semiconductor element of the present inventionmore preferably includes a coating step of coating a substrate with theorganic semiconductor composition of the present invention and aremoving step of removing at least a portion of the solvent from thecoated organic semiconductor composition.

The organic semiconductor composition according to the present inventiondescribed below preferably includes a solvent and more preferablyincludes a solvent having a boiling point of 100° C. or higher.

As the solvent, well-known solvents can be used.

Specifically, examples thereof include a hydrocarbon-based solvent suchas hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene,decalin, and 1-methylnaphthalene, a ketone-based solvent such asacetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone,a halogenated hydrocarbon-based solvent such as dichloromethane,chloroform, tetrachloromethane, dichloroethane, trichloroethane,tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, anester-based solvent such as ethyl acetate, butyl acetate, and amylacetate, an alcohol-based solvent such as methanol, propanol, butanol,pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve,and ethylene glycol, an ether-based solvent such as dibutyl ether,tetrahydrofuran, dioxane, and anisole, an amide-based solvent such asN,N-dimethylformamide and N,N-dimethylacetamide, an imide-based solventsuch as 1-methyl-2-pyrrolidone and 1-methyl-2-imidazolidinone, asulfoxide-based solvent such as dimethylsulfoxide, and a nitrile-basedsolvent such as acetonitrile.

In order to obtain stability of an organic semiconductor compositiondescribed below and to form an even film, a boiling point of the solventin normal pressure is preferably 100° C. or higher, more preferably 150°C. or higher, even more preferably 175° C. or higher, and particularlypreferably 200° C. or higher.

In order to dry the solvent, after the organic semiconductor compositionis applied, the boiling point of the solvent in normal pressure ispreferably 300° C. or lower, more preferably 250° C. or lower, and evenmore preferably 220° C. or lower.

Unless described otherwise, according to the present invention, theboiling point is a boiling point in normal pressure.

The solvent may be used singly or two or more types thereof may be usedin combination.

Among these, a hydrocarbon-based solvent, a halogenatedhydrocarbon-based solvent, and/or an ether-based solvent are preferable,and toluene, xylene, mesitylene, tetralin, dichlorobenzene and anisoleare more preferable.

In a case where the solvent is contained, the content of the compoundrepresented by in Formula 1 in the organic semiconductor composition ofthe present invention is preferably 20 mass % or less, more preferably0.01 to 20 mass %, even more preferably 0.05 to 10 mass %, andparticularly preferably 0.1 to 5 mass %. In a case where the binderpolymer and the solvent are contained, the content of the binder polymerin the organic semiconductor composition according to the presentinvention is preferably 0.01 to 80 mass %, more preferably 0.05 to 10mass %, and even more preferably 0.1 to 5 mass %. If the content is inthe range described above, coating properties are excellent, and thus anorganic semiconductor film can be easily formed.

The drying treatment in the removing step is a treatment performed ifnecessary, and the optimal treatment conditions are appropriatelyselected according to the type of the specific compound and the solventused. In view of further improving mobility and heat resistance of theobtained organic semiconductor and improving productivity, a heatingtemperature is preferably 30° C. to 100° C. and more preferably 40° C.to 80° C., and a heating time is preferably 10 to 300 minutes and morepreferably 30 to 180 minutes.

A thickness of the formed semiconductor active layer is not particularlylimited. From the viewpoint of mobility and heat resistance of theobtained organic semiconductor, the film thickness is preferably 10 to500 nm and more preferably 30 to 200 nm.

The organic semiconductor element is not particularly limited, but ispreferably an organic semiconductor element having 2 to 5 terminals, andmore preferably an organic semiconductor element having 2 or 3terminals.

It is preferable that the organic semiconductor element is not aphotoelectric conversion element.

The organic semiconductor element according to the present invention ispreferably a non-luminous organic semiconductor element.

Examples of a 2-terminal element include a rectifier diode, a constantvoltage diode, a PIN diode, a Schottky barrier diode, a surge protectiondiode, a diac, a varistor, a tunnel diode, and the like.

Examples of a 3-terminal element include a bipolar transistor, aDarlington transistor, a field effect transistor, insulated gate bipolartransistor, a uni-junction transistor, a static induction transistor, agate turn-off thyristor, a triac, a static induction thyristor, and thelike.

Among these, a rectifier diode and transistors are preferable, and afield effect transistor is more preferable.

As the field effect transistor, an organic thin film transistor ispreferable.

An aspect of the organic thin film transistor of the present inventionwill be described with reference to drawings.

FIG. 1 is a schematic cross-sectional view of an aspect of an organicsemiconductor element (organic thin film transistor (organic TFT)) ofthe present invention.

In FIG. 1, an organic thin film transistor 100 comprises a substrate 10,a gate electrode 20 disposed on the substrate 10, a gate insulating film30 covering the gate electrode 20, a source electrode 40 and a drainelectrode 42 which contact a surface of the gate insulating film 30 thatis on the side opposite to the gate electrode 20 side, an organicsemiconductor film 50 covering a surface of the gate insulating film 30between the source electrode 40 and the drain electrode 42, and asealing layer 60 covering each member. The organic thin film transistor100 is a bottom gate-bottom contact type organic thin film transistor.

In FIG. 1, the organic semiconductor film 50 corresponds to a filmformed of the composition described above.

Hereinafter, the substrate, the gate electrode, the gate insulatingfilm, the source electrode, the drain electrode, the sealing layer, andmethods for forming each of these will be specifically described.

<Substrate>

The substrate plays a role of supporting the gate electrode, the sourceelectrode, the drain electrode, and the like which will be describedlater.

The type of the substrate is not particularly limited, and examplesthereof include a plastic substrate, a glass substrate, a ceramicsubstrate, and the like. Among these, from the viewpoint ofapplicability to each device and costs, a glass substrate or a plasticsubstrate is preferable.

Examples of materials of the plastic substrate include a thermosettingresin (for example, an epoxy resin, a phenol resin, a polyimide resin,or a polyester resin (for example, polyethylene terephthalate (PET) orpolyethylene naphthalate (PEN)) and a thermoplastic resin (for example,a phenoxy resin, a polyethersulfone, polysulfone, or polyphenylenesulfone).

Examples of materials of the ceramic substrate include alumina, aluminumnitride, zirconia, silicon, silicon nitride, silicon carbide, and thelike.

Examples of materials of the glass substrate include soda lime glass,potash glass, borosilicate glass, quartz glass, aluminosilicate glass,lead glass, and the like.

<Gate Electrode, Source Electrode, and Drain Electrode>

Examples of materials of the gate electrode, the source electrode, andthe drain electrode include a metal such as gold (Au), silver, aluminum(Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum,magnesium, calcium, barium, or sodium; a conductive oxide such as InO₂,SnO₂, or indium tin oxide (ITO); a conductive polymer such aspolyaniline, polypyrrole, polythiophene, polyacetylene, orpolydiacetylene; a semiconductor such as silicon, germanium, or galliumarsenide; a carbon material such as fullerene, carbon nanotubes, orgraphite; and the like. Among these, a metal is preferable, and silverand aluminum are more preferable.

A thickness of each of the gate electrode, the source electrode, and thedrain electrode is not particularly limited, but is preferably 20 to 200nm.

A method of forming the gate electrode, the source electrode, and thedrain electrode is not particularly limited, but examples thereofinclude a method of vacuum vapor-depositing or sputtering an electrodematerial onto a substrate, a method of coating a substrate with acomposition for forming an electrode, a method of printing a compositionfor forming an electrode onto a substrate, and the like. Furthermore, ina case where the electrode is patterned, examples of the patterningmethod include a photolithography method; a printing method such as inkjet printing, screen printing, offset printing, or relief printing; amask vapor deposition method; and the like.

<Gate Insulating Film>

Examples of materials of the gate insulating film include a polymer suchas polymethyl methacrylate, polystyrene, polyvinylphenol, polyimide,polycarbonate, polyester, polyvinylalcohol, polyvinyl acetate,polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, an epoxyresin, or a phenol resin; an oxide such as silicon dioxide, aluminumoxide, or titanium oxide; a nitride such as silicon nitride; and thelike. Among these materials, in view of the compatibility with theorganic semiconductor film, a polymer is preferable.

In a case where a polymer is used as the material of the gate insulatingfilm, it is preferable to use a cross-linking agent (for example,melamine) in combination. If the cross-linking agent is used incombination, the polymer is cross-linked, and durability of the formedgate insulating film is improved.

A film thickness of the gate insulating film is not particularlylimited, but is preferably 100 to 1,000 nm.

A method of forming the gate insulating film is not particularlylimited, but examples thereof include a method of coating a substrate,on which the gate electrode is formed, with a composition for forming agate insulating film, a method of vapor-depositing or sputtering thematerial of the gate insulating film onto a substrate on which the gateelectrode is formed, and the like. A method of coating theaforementioned substrate with the composition for forming a gateinsulating film is not particularly limited, and it is possible to use aknown method (a bar coating method, a spin coating method, a knifecoating method, or a doctor blade method).

In a case where the gate insulating film is formed by coating thesubstrate with the composition for forming a gate insulating film, forthe purpose of removing the solvent, causing cross-linking, or the like,the composition may be heated (baked) after coating.

<Binder Polymer Layer>

The organic semiconductor element of the present invention preferablyhas a layer of the aforementioned binder polymer between thesemiconductor active layer and an insulating film, and more preferablyhas a layer of the aforementioned binder polymer between thesemiconductor active layer and the gate insulating film. A filmthickness of the binder polymer layer is not particularly limited, butis preferably 20 to 500 nm. The binder polymer layer should be a layercontaining the aforementioned polymer, and is preferably a layercomposed of the aforementioned binder polymer.

A method of forming the binder polymer layer is not particularlylimited, and a known method (a bar coating method, a spin coatingmethod, a knife coating method, a doctor blade method, or an ink jetmethod) can be used.

In a case where the binder polymer layer is formed by performing coatingby using a composition for forming a binder polymer layer, for thepurpose of removing a solvent, causing cross-linking, or the like, thecomposition may be heated (baked) after coating.

The binder polymer layer is preferably a binder polymer layer that canbe formed together with a semiconductor active layer from the organicsemiconductor composition according to the present invention.

<Sealing Layer>

From the viewpoint of durability, the organic semiconductor element ofthe present invention preferably comprises a sealing layer as anoutermost layer. In the sealing layer, a known sealant can be used.

A thickness of the sealing layer is not particularly limited, but ispreferably 0.2 to 10 μm.

A method of forming the sealing layer is not particularly limited, butexamples thereof include a method of coating a substrate, on which thegate electrode, the gate insulating film, the source electrode, thedrain electrode, and the organic semiconductor film are formed, with acomposition for forming a sealing layer, and the like. Specific examplesof the method of coating the substrate with the composition for forminga sealing layer are the same as the examples of the method of coatingthe substrate with the composition for forming a gate insulating film.In a case where the organic semiconductor film is formed by coating thesubstrate with the composition for forming a sealing layer, for thepurpose of removing the solvent, causing cross-linking, or the like, thecomposition may be heated (baked) after coating.

FIG. 2 is a schematic cross-sectional view of another aspect of theorganic semiconductor element (organic thin film transistor) of thepresent invention.

In FIG. 2, an organic thin film transistor 200 comprises the substrate10, the gate electrode 20 disposed on the substrate 10, the gateinsulating film 30 covering the gate electrode 20, the organicsemiconductor film 50 disposed on the gate insulating film 30, thesource electrode 40 and the drain electrode 42 disposed on the organicsemiconductor film 50, and the sealing layer 60 covering each member.Herein, the source electrode 40 and the drain electrode 42 are formedusing the aforementioned composition of the present invention. Theorganic thin film transistor 200 is a bottom gate-top contact typeorganic thin film transistor.

The substrate, the gate electrode, the gate insulating film, the sourceelectrode, the drain electrode, the organic semiconductor film, and thesealing layer are as described above.

In FIGS. 1 and 2, the aspects of the bottom gate-bottom contact typeorganic thin film transistor and the bottom gate-top contact typeorganic thin film transistor were specifically described. However, theorganic semiconductor element of the present invention can also suitablyused in a top gate-bottom contact type organic thin film transistor anda top gate-top contact type organic thin film transistor.

The organic thin film transistor described above can be suitably usedfor electronic paper and a display device.

(Organic Semiconductor Composition)

The organic semiconductor composition according to the present inventionis an organic semiconductor composition containing the compoundrepresented by Formula 1 below and a solvent, the compound representedby Formula 1 below and the solvent having a boiling point of 100° C. orhigher are contained, and a content of the compound represented byFormula 1 below is preferably 20 mass % or less with respect to a totalamount of the organic semiconductor composition.

In Formula 1, A represents a central aromatic ring and is an aromaticring selected from any one of aromatic rings represented by Formula 2 or3, *'s represent bonding positions to two side chalcogenophene rings,and X^(a)'s represent chalcogen atoms,

one of X¹ and Y¹ is a chalcogen atom and the other is C(R^(a)), one ofX² and Y² is a chalcogen atom and the other is C(R^(b)), R^(a)'s eachindependently represent a hydrogen atom or R¹, R^(b)'s eachindependently represent a hydrogen atom or R², in a case where A is anaromatic ring represented by Formula 3, Y¹ and Y² each independently area chalcogen atom, X¹ is C(R^(a)), and X² is C(R^(b)),

p and q each independently represent an integer of 0 to 2, Z's eachindependently represent a hydrogen atom or a halogen atom, and R¹ and R²each independently represent a halogen atom or a group represented byFormula W below.—S-L-T  (W)

In Formula W, S represents a single bond or —(C(R^(S))₂)_(n)—, R^(S)'seach independently represent a hydrogen atom or a halogen atom, nrepresents an integer of 1 to 17, L represents a single bond, a divalentlinking group represented by any one of Formulae L-1 to L-15 below, or adivalent linking group obtained by bonding two or more divalent linkinggroups represented by any one of Formulae L-1 to L-15 below, and Trepresents an alkyl group, a haloalkyl group, a cyano group, a vinylgroup, an ethynyl group, an aryl group, a heteroaryl group, anoxyethylene group, an oligooxyethylene group in which a repetitionnumber of oxyethylene units is 2 or greater, a siloxane group, anoligosiloxane group having two or more silicon atoms, or a trialkylsilylgroup.

In Formulae L-1 to L-15, a wavy line portion represents a bondingposition to S or another divalent linking group represented by any oneof Formulae L-1 to L-15, * represents a bonding position to T or anotherdivalent linking group represented by any one of Formulae L-1 to L-15, min Formula L-13 represents an integer of 0 to 4, m's in Formulae L-14and L-15 each represent an integer of 0 to 2, R″s in Formulae L-1 andL-2 each independently represent a hydrogen atom or a substituent, andR″'s in Formulae L-13, L-14, and L-15 each independently represent asubstituent.

The organic semiconductor composition according to the presentpreferably contains a binder polymer.

The compound represented by Formula 1 and the binder polymer in theorganic semiconductor composition according to the present invention isthe same as the compound represented by Formula 1 and the binder polymerdescribed above, and preferable aspects are also the same.

<Solvent Having Boiling Point of 100° C. or Higher>

The organic semiconductor composition according to the present inventioncontains a solvent having a boiling point of 100° C. or higher.

Examples of the solvent having a boiling point of 100° C. or higherinclude a hydrocarbon-based solvent such as octane, decane, toluene,xylene, mesitylene, ethylbenzene, decalin, 1-methylnaphthalene,tetralin, and dimethyltetralin, a ketone-based solvent such as methylisobutyl ketone and cyclohexanone, a halogenized hydrocarbon-basedsolvent such as tetrachloroethane, chlorobenzene, dichlorobenzene,chlorotoluene, 1-fluoronaphthalene, and 1-chloronaphthalene, anester-based solvent such as butyl acetate and amyl acetate, analcohol-based solvent such as butanol, pentanol, hexanol, cyclohexanol,methyl cellosolve, ethyl cellosolve, and ethylene glycol, an ether-basedsolvent such as dibutyl ether, dioxane, anisole, 4-tertiary butylanisole, and m-dimethoxybenzene, an amide-based solvent such asN,N-dimethylformamide and N,N-dimethylacetamide, an imide-based solventsuch as 1-methyl-2-pyrrolidone and 1-methyl-2-imidazolidinone, asulfoxide-based solvent such as dimethylsulfoxide, a nitrile-basedsolvent such as butyronitrile and benzonitrile.

The solvent having a boiling point of 100° C. or higher may be usedsingly or two or more types thereof may be used in combination.

Among these, a hydrocarbon-based solvent, a halogenizedhydrocarbon-based solvent, and/or an ether-based solvent is preferable,and toluene, xylene, mesitylene, tetralin, dichlorobenzene, or anisoleare more preferable. If the solvent is as described above, coatingproperties are excellent, and thus an organic semiconductor film can beeasily formed.

The organic semiconductor composition according to the present inventionmay contain a solvent having a boiling point of lower than 100° C., butthe content thereof is preferably less than the content of the solventhaving a boiling point of 100° C. or higher, and more preferably 1/10 orless of the content of the solvent having a boiling point of 100° C. orhigher. It is even more preferable that a solvent having a boiling pointof less than 100° C. is not contained.

In order to obtain stability of an organic semiconductor composition andto form an even film, a boiling point of the solvent having a boilingpoint of 100° C. or higher in normal pressure is preferably 150° C. orhigher, more preferably 175° C. or higher, and particularly preferably200° C. or higher. In order to dry the specific solvent after an organicsemiconductor ink is applied, the boiling point of the specific solventis preferably 300° C. or lower, more preferably 250° C. or lower, andeven more preferably 220° C. or lower.

The content of the solvent having a boiling point of 100° C. or higherin the organic semiconductor composition according to the presentinvention is preferably 50 to 99.9 mass %, more preferably 80 to 99.5mass %, and even more preferably 90 to 99.0 mass % with respect to atotal mass of the organic semiconductor composition.

The organic semiconductor composition according to the present inventionmay include other components in addition to the compound represented byFormula 1, the binder polymer, and the solvent.

As the components, well-known additives may be used.

The content of the component in addition to the compound represented byFormula 1, the binder polymer, and the solvent in the composition forforming the organic semiconductor according to the present invention ispreferably 10 mass % or less, more preferably 5 mass % or less, evenmore preferably 1 mass % or less, and particularly preferably 0.1 mass %or less with respect to the total solid content. If the content is inthe range described above, film formability is improved, and mobilityand heat resistance of the obtained organic semiconductor are furtherimproved. The solid content is an amount of the components excluding thevolatilizable component such as the solvent.

The viscosity of the organic semiconductor composition according to thepresent invention is not particularly limited. However, in view ofexcellent coating properties, the viscosity is preferably 3 to 100mPa·s, more preferably 5 to 50 mPa·s, and even more preferably 9 to 40mPa·s. The viscosity according to the present invention refers toviscosity at 25° C.

As a method of measuring the viscosity, a measuring method in conformityof JIS Z8803 is preferable.

In the organic semiconductor composition according to the presentinvention, it is preferable that at least a portion of the compoundrepresented by Formula 1 is dissolved, and it is more preferable thatthe entire compound is dissolved. However, a portion thereof may bedispersed without being dissolved.

The content of the compound represented by Formula 1 according to thepresent invention is preferably 20 mass % or less, more preferably 0.001to 20 mass %, even more preferably 0.001 to 15 mass %, and particularlypreferably 0.01 to 10 mass % with respect to a total amount of theorganic semiconductor composition. In a case where two or more types ofcompound represented by Formula 1 are used together, the total contentof the compound represented by Formula 1 is preferably in the rangedescribed above. If the content of the compound represented by Formula 1is in the range described above, carrier mobility is more excellent, andpreservation stability is also excellent.

The content of the compound represented by Formula 1 is preferably 30 to99 mass %, more preferably 50 to 95 mass %, and even more preferably 70to 90 mass % with respect to a total solid content.

The method of manufacturing the organic semiconductor compositionaccording to the present invention is not particularly limited, andwell-known methods can be applied. For example, the compound representedby Formula 1 in a predetermined amount is added to the solvent having aboiling point of 100° C. or higher, a stirring treatment can be suitablyperformed, so as to obtain a desired composition. In a case where thebinder polymer is used, it is suitable that the compound represented byFormula 1 and the binder polymer are simultaneously or sequentiallyadded, so as to manufacture the composition.

(Organic Semiconductor Film)

The organic semiconductor film according to the present inventioncontains the compound represented by Formula 1.

It is preferable that the organic semiconductor film according to thepresent invention is an organic semiconductor film formed from theorganic semiconductor compositions according to the present invention.

The organic semiconductor film according to the present inventionpreferably contains the binder polymer.

The compound represented by Formula 1 and the binder polymer in theorganic semiconductor film according to the present invention are thesame as the compound represented by Formula 1 and the binder polymerdescribed above in the organic semiconductor element according to thepresent invention and preferable aspects thereof are also the same.

The organic semiconductor film according to the present invention mayinclude other components in addition to the compound represented byFormula 1 and the binder polymer.

As the component, well-known additives may be used.

The content of the component in addition to the compound represented byFormula 1 and the binder polymer in the organic semiconductor filmsaccording to the present invention preferably 10 mass % or less, morepreferably 5 mass % or less, even more preferably 1 mass % or less, andparticularly preferably 0.1 mass % or less. If the content is in therange above, film formability is improved, and mobility and heatresistance of the obtained organic semiconductor are further improved.The solid content is an amount of components other than thevolatilizable components such as the solvent.

The film thickness of the organic semiconductor film according to thepresent invention is not particularly limited. However, in view ofmobility and heat resistance of the obtained organic semiconductor, thefilm thickness is preferably 10 to 500 nm and more preferably 30 to 200nm.

The organic semiconductor film according to the present invention can besuitably used in the organic semiconductor element, and can beparticularly suitably used in the organic transistor (organic thin filmtransistor).

(Organic Semiconductor Compound)

The organic semiconductor compound according to the present invention isrepresented by Formula 1 below.

In Formula 1, A represents a central aromatic ring and is an aromaticring selected from any one of aromatic rings represented by Formula 2 or3, *'s represent bonding positions to two side chalcogenophene rings,and X^(a)'s represent chalcogen atoms,

one of X¹ and Y¹ is a chalcogen atom and the other is C(R^(a)), one ofX² and Y² is a chalcogen atom and the other is C(R^(b)), R^(a)'s eachindependently represent a hydrogen atom or R¹, R^(b)'s eachindependently represent a hydrogen atom or R², in a case where A is anaromatic ring represented by Formula 3, Y¹ and Y² are each independentlya chalcogen atom, X¹ represents C(R^(a)), and X² represents C(R^(b)),

p and q each independently represent an integer of 0 to 2, Z's eachindependently represent a hydrogen atom or a halogen atom, and R¹ and R²each independently represent a halogen atom or a group represented byFormula W below.—S-L-T  (W)

In Formula W, S represents a single bond or —(C(R^(S))₂)_(n)—, R^(S)'seach independently represent a hydrogen atom or a halogen atom, nrepresents an integer of 1 to 17, L represents a single bond, a divalentlinking group represented by any one of Formulae L-1 to L-15 below, or adivalent linking group obtained by bonding two or more divalent linkinggroups represented by any one of Formulae L-1 to L-15 below, and Trepresents an alkyl group, a haloalkyl group, a cyano group, a vinylgroup, an ethynyl group, an aryl group, a heteroaryl group, anoxyethylene group, an oligooxyethylene group in which a repetitionnumber of oxyethylene units is 2 or greater, a siloxane group, anoligosiloxane group having two or more silicon atoms, or a trialkylsilylgroup.

In Formulae L-1 to L-15, a wavy line portion represents a bondingposition to S or another divalent linking group represented by any oneof Formulae L-1 to L-15, * represents a bonding position to T or anotherdivalent linking group represented by any one of Formulae L-1 to L-15, min Formula L-13 represents an integer of 0 to 4, m's in Formulae L-14and L-15 each represent an integer of 0 to 2, R″s in Formulae L-1 andL-2 each independently represent a hydrogen atom or a substituent, andR″'s in Formulae L-13, L-14, and L-15 each independently represent asubstituent.

The compound represented by Formula 1 in the organic semiconductorcompound according to the present invention is the same as the compoundrepresented by Formula 1 described below, and the preferable aspects arethe same.

In view of synthesization, examples thereof is preferably a compoundrepresented by Formula 1-2 or 1-3 above and more preferably a compoundrepresented by Formula 1-5 or 1-6 above.

EXAMPLES

Hereinafter, the present invention will be more specifically describedbased on examples. The materials and the amount thereof used, theproportion of the materials, the content and procedure of treatments,and the like described in the following examples can be appropriatelychanged within a scope that does not depart from the gist of the presentinvention. Accordingly, the scope of the present invention is notlimited to the following specific examples. Herein, unless otherwisespecified, “part” and “%” are based on mass.

Compounds A-1 to A-7 represented by Formula 1 and Comparative CompoundsA′-1 to A′-9 which were used in examples and comparative examples areprovided below.

Synthesization Example

An intermediate M1 was synthesized by Scheme X1 below.

LDA: Lithium diisopropylamide (manufactured by Tokyo Chemical IndustryCo., Ltd.)

TMSCl: Trimethylsilyl chloride (manufactured by Wako Pure ChemicalIndustries, Ltd.)

THF: Tetrahydrofuran (manufactured by Wako Pure Chemical Industries,Ltd.)

Br₂: Bromine (manufactured by Wako Pure Chemical Industries, Ltd.)

CH₂Cl₂: Dichloromethane (manufactured by Wako Pure Chemical Industries,Ltd.)

3-mercaptothiophene: manufactured by Tokyo Chemical Industry Co., Ltd.

K₂CO₃: Potassium carbonate (manufactured by Tokyo Chemical Industry Co.,Ltd.)

NMP: N-methylpyrrolidone (manufactured by Kanto Chemical Co., Inc.)

H₂O₂: Hydrogen peroxide (manufactured by Kanto Chemical Co., Inc.)

MTO-Re: Methylrhenium trioxide (manufactured by Wako Pure ChemicalIndustries, Ltd.)

CH₃CN: Acetonitrile (manufactured by Wako Pure Chemical Industries,Ltd.)

Pd(OAc)₂: Palladium acetate (II) (manufactured by Wako Pure ChemicalIndustries, Ltd.)

KOAc: Potassium acetate (manufactured by Wako Pure Chemical Industries,Ltd.)

DMAc: Dimethylacetamide (manufactured by Wako Pure Chemical Industries,Ltd.)

KI: Potassium iodide (manufactured by Wako Pure Chemical Industries,Ltd.)

p-TSA.H₂O: p-toluenesulfonic acid monohydrate (manufactured by Wako PureChemical Industries, Ltd.)

Lithium 2,2,6,6-tetramethylpiperidide: Synthesized by dissolvingtetramethylpiperidine (manufactured by Wako Pure Chemical Industries,Ltd.) in THF and dropwise adding n-butyllithium (manufactured by KantoChemical Co., Inc.) at 0° C.

1,2-dibromo-1,1,2,2-tetrachloroethane: manufactured by Wako PureChemical Industries, Ltd.

Dry THF: Dry tetrahydrofuran (manufactured by Wako Pure ChemicalIndustries, Ltd.)

An intermediate 2 below was synthesized in the same manner as the thirdprocess of Scheme X1 above except for using 2-mercaptothiophene insteadof 3-mercaptothiophene.

An intermediate 3 below was synthesized in the same manner as the thirdprocess of Scheme X1 above except for using2,5-dibromo-3,4-difluorothiophene instead of1,4-dibromo-2,3-difluorobenzene and using 2-mercaptothiophene instead of3-mercaptothiophene. 2,5-Dibromo-3,4-difluorothiophene was synthesizedin a method disclosed in Journal of the American Chemical Society, 2001,vol. 123, #19, p. 4643-4644.

A compound A-1 used in Example 1 was synthesized by Scheme X2 below.

Pd-XPhos (G3):(2-Dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate (manufactured by Sigma-Aldrich Co. LLC.)

A compound A-2 used in Example 2 was synthesized by using anintermediate 2 instead of the intermediate 1 in Scheme X2 above.

A compound A-3 used in Example 3 was synthesized in the same manner asScheme X2 above except for using an intermediate 3 instead of theintermediate 1.

A compound A-4 used in Example 4 was synthesized by Scheme X3 below.

Pd(PPh₃)₄: Tetrakistriphenylphosphine palladium (0) (manufactured byTokyo Chemical Industry Co., Ltd.)

A compound A-5 used in Example 5 was synthesized in the same manner asScheme X3 above except for using 4-(4-butoxybutyl) phenylboronic acidinstead of 4-dodecylphenylboronic acid.

A compound A-6 used in Example 6 was synthesized by Scheme X4 below bysynthesizing an intermediate M4 below by using equal amounts of Li-TMPand 1,1,2,2-tetrachloro-1,2-dibromoethane used in the final step ofScheme X1 above in the half amount used in the synthesization of theintermediate 1 and using an obtained intermediate M4.

A compound A-7 used in Example 7 was synthesized by Scheme X5 below.

Examples 1 to 7 and Comparative Examples 1 to 9

<Manufacturing of FET Elements>

Compounds (each 1 mg) presented in Table 11 and toluene (1 mL) weremixed and heated to 100° C., so as to obtain an organic semiconductorcomposition. Under the nitrogen atmosphere, this composition was castedto a substrate for measuring FET characteristics heated to 90° C. undernitrogen atmosphere so as to form an organic semiconductor film(thickness: 200 nm), and an organic thin film transistor element formeasuring FET characteristics was obtained. As the substrate formeasuring FET characteristics, a silicon substrate in a bottomgate⋅bottom contact structure including chromium/gold (gate width W=100mm, gate length L=100 μm) arranged in a comb-shape as source and drainelectrodes and SiO₂ (film thickness: 200 nm) as an insulating film wasused.

<Evaluation of Carrier Mobility>

With respect to the FET characteristics of the organic thin filmtransistor elements of the respective examples and the respectivecomparative examples, carrier mobility was evaluated under normalpressure and the nitrogen atmosphere by employing a semiconductorparameter analyzer (manufactured by Agilent, 4156C) to which a semiautomatic prober (manufactured by Vector Semiconductor Co., Ltd.,AX-2000) was connected.

Carrier mobility μ was calculated by applying a voltage of −80V betweensource electrodes-drain electrodes of the respective organic thin filmtransistor elements (FET elements), changing gate voltages in the rangeof +20 V to −100 V, and using an equation below indicating a draincurrent I_(d).I _(d)=(w/2L)μC _(i)(V _(g) −V _(th))²

In the equation, L represents a gate length, w represents a gate width,C_(i) represents capacity per unit area of an insulating layer, V_(g)represents a gate voltage, and V_(th) represents a threshold voltage.

<Coating Film Formability Evaluation>

The compounds (each 1 mg) presented in Table 11 and toluene (1 mL) weremixed and heated to 100° C., so as to obtain organic semiconductorcompositions. Under the nitrogen atmosphere, these compositions werecasted to entire surfaces of substrates on which channels for 50elements were formed and which were heated to 90° C. so as to formorganic semiconductor thin films, and 50 elements of organic thin filmtransistor elements for measuring FET characteristics were obtained.

—Evaluation Standard—

Coating film formability A: 45 or more (90% or greater) elements weredriven as TFT elements among the obtained 50 elements.

Coating film formability B: Less than 45 (less than 90%) elements weredriven as TFT elements among the obtained 50 elements.

<Evaluation of Qualities of Coating Film>

Qualities of the coating film were evaluated by the method describedbelow.

With respect to the semiconductor active layer of the organic thin filmtransistor element, a domain size was measured using a polarizingmicroscope in the range of 1 mm square, so as to calculate an averagedomain size. The obtained result was evaluated in five stages below. Inpractice, Evaluation D does not have problems, but Evaluation A, B, or Cis preferable, Evaluation A or B is more preferable, and Evaluation A isparticularly preferable.

A: An average domain size is greater than 5 micrometers.

B: An average domain size is greater than 1 micrometer and 5 micrometersor less.

C: An average domain size is greater than 0.5 micrometers and 1micrometer or less.

D: An average domain size is 0.5 micrometers or less.

E: A film was not continuous and evaluation was not able to beperformed.

<Heat Resistance Evaluation>

After the manufactured respective organic thin film transistor elementswere heated for one hour at 130° C. in a nitrogen glove box, carriermobility μ was measured, so as to calculate a carrier mobilitymaintenance rate after heating by the equation below.Carrier mobility maintenance rate after heating (%)=Mobility (afterheating)/Mobility (initial value)

Obtained results were evaluated according to evaluation standards below.

—Evaluation Standard—

A: 95% or greater.

B: 70% or greater and less than 95%.

C: 40% or greater and less than 70%.

D: 20% or greater and less than 40%.

E: Less than 20%.

<Fold Resistance (Flexibility) Evaluation>

Each organic thin film transistor element that was manufactured on apolyethylene naphthalate (PEN) film (TEONEX 65H manufactured by TeijinDuPont Films Japan Limited) was subjected to a 100 times folding testwith a curvature radius of four millimeters, carrier mobility μ wasmeasured, a carrier mobility maintenance rate after the folding test wascalculated by an equation below.Carrier mobility maintenance rate (%) after folding test=mobility (afterfolding)/mobility (initial value)

The obtained result was evaluated according to the evaluation standardbelow.

—Evaluation Standard—

A: 95% or greater

B: 90% or greater and less than 95%

C: Less than 90%

In practice, Evaluation A or B is required, and Evaluation A ispreferable.

TABLE 11 Mobility (Toluene Coating film Quality of Heat Fold Compoundsolution) formability coating film resistance resistance Example 1 A-10.51 A A A A Example 2 A-2 0.23 A A A A Example 3 A-3 0.15 A A A AExample 4 A-4 7 × 10⁻² A B A A Example 5 A-5 5 × 10⁻² A B A B Example 6A-6 2 × 10⁻² A C B A Example 7 A-7 1 × 10⁻² A C B B Comparative A′-1 2 ×10⁻⁴ B D C C Example 1 Comparative A′-2 3 × 10⁻⁵ B D C D Example 2Comparative A′-3 No TFT B D C D Example 3 Characteristics ComparativeA′-4 No TFT B E N/A N/A Example 4 Characteristics Comparative A′-5 NoTFT B E N/A N/A Example 5 Characteristics Comparative A′-6 No TFT B EN/A N/A Example 6 Characteristics Comparative A′-7 No TFT B D N/A N/AExample 7 Characteristics Comparative A′-8 No TFT B E N/A N/A Example 8Characteristics Comparative A′-9 No TFT B E N/A N/A Example 9Characteristics

In Table 11 and Table 12 provided below, N/A represents that evaluationwas not able to be performed, since TFT characteristics were notprovided, and mobility was not able to be measured.

Examples 8 to 11, and Comparative Examples 10 and 11: Binder PolymerAddition Example

The organic semiconductor compositions and the organic thin filmtransistor elements of Examples 8 to 11 and Comparative Examples 10 and11 were manufactured in the same manner as Examples 1 to 7 andComparative Examples 1 to 9 except for mixing Compounds in Table 12 orComparative Compounds (each 1 mg), 1 mg of PαMS (poly(α-methylstyrene),Mw=300,000, manufactured by Sigma-Aldrich Co. LLC.), and toluene (1 mL),heating the same to 100° C., and using the resultant as a coatingsolution, and various evaluations were performed. Evaluation results arepresented in Table 12.

TABLE 12 Binder Mobility (Toluene Coating film Quality of Heat FoldCompound polymer solution) formability coating film resistanceresistance Example 8 A-1 PαMS 0.75 A A A A Example 9 A-1 PαMS 0.3  A A AA Example 10 A-1 PαMS 0.22 A A A A Example 11 A-5 PαMS 1.2 × 10⁻¹ A A AA Comparative A′-5 PαMS No TFT B E N/A N/A Example 10 CharacteristicsComparative A′-9 PαMS No TFT B E N/A N/A Example 11 Characteristics

Examples 12 to 22 and Comparative Examples 12 to 22: Ink Jet Coating

The organic semiconductor composition manufactured for the coating filmformability evaluation was applied to a substrate for measuring FETcharacteristics by an ink jet printing. Specifically, DPP2831(manufactured by FUJIFILM Global Graphic Systems Co., Ltd.) was used asan inkjet device and 10 pL heads were used, so as to form a solid filmwith a jetting frequency of 2 Hz and a pitch between dots of 20 μm.Thereafter, drying was performed for one hour at 70° C., so as to forman organic semiconductor film, and the organic TFT element for measuringFET characteristics was obtained.

In the examples and the comparative examples, all of the evaluations ofcarrier mobility, coating film formability, heat resistance, and foldingresistance described below with respect to the organic TFT elements thatwere able to be obtained by ink jet printing were the same as theevaluations of the organic TFT elements that were able to be obtained bya cast method.

Even in a case where the organic semiconductor film was patterned in achannel area by an ink jet method, performances were the same as in theelement manufactured by a cast method or a solid film elementmanufactured by an ink jet method.

Examples 23 to 33 and Comparative Examples 23 to 33: FlexographicPrinting

The substrate above on which source-drain electrodes were formed wascoated with the organic semiconductor composition manufactured in thecoating film formability evaluation above by a flexographic printingmethod. As the printing device, a flexographic printability test machineF1 (manufactured by IGT Testing Systems) was used as a printing machine,and AFP DSH 1.70% (manufactured by Asahi Kasei Corporation)/a solidimage was used as a flexographic resin version. After printing wasperformed in a pressure between a plate and a substrate of 60 N and atransportation speed of 0.4 m/second, drying was performed at 40° C. fortwo hours, so as to manufacture a semiconductor active layer.

With respect to the respective examples or comparative examples, all ofthe evaluations of carrier mobility, coating film formability, heatresistance, and folding resistance of the organic TFT elements that wereable to be obtained by a flexographic printing described below were thesame as the evaluations of the organic TFT elements that were able to beobtained by a cast method.

Example 34

The organic semiconductor composition and the organic thin filmtransistor element were manufactured in the same manner as in Examples 1to 33 except for using anisole or tetralin instead of toluene as thesolvent, respectively, and evaluation was performed. Characteristics andevaluation results which were the same as those in the correspondingexamples were able to be obtained.

EXPLANATION OF REFERENCES

-   -   10: substrate    -   20: gate electrode    -   30: gate insulating film    -   40: source electrode    -   42: drain electrode    -   50: organic semiconductor film    -   60: sealing layer    -   100, 200: organic thin film transistor

What is claimed is:
 1. An organic semiconductor element comprising: acompound represented by Formula 1 below in a semiconductor active layer,

in Formula 1, A represents a central aromatic ring and is an aromaticring selected from any one of aromatic rings represented by Formula 2 or3, *'s represent bonding positions to two side chalcogenophene rings,and X^(a)'s represent chalcogen atoms, one of X¹ and Y¹ is a chalcogenatom and the other is C(R^(a)), one of X² and Y² is a chalcogen atom andthe other is C(R^(b)), R^(a)'s each independently represent a hydrogenatom or R¹, R^(b)'s each independently represent a hydrogen atom or R²,in a case where A is an aromatic ring represented by Formula 3, Y¹ andY² are each independently a chalcogen atom, X¹ is C(R^(a)), and X² isC(R^(b)), p and q each independently represent an integer of 0 to 2, Z'seach independently represent a hydrogen atom or a halogen atom, and R¹and R² each independently represent a halogen atom or a grouprepresented by Formula W below,—S-L-T  (W) in Formula W, S represents a single bond or—(C(R^(S))₂)_(n)—, R^(S)'s each independently represent a hydrogen atomor a halogen atom, n represents an integer of 1 to 17, L represents asingle bond, a divalent linking group represented by any one of FormulaeL-1 to L-15 below, or a divalent linking group obtained by bonding twoor more divalent linking groups represented by any one of Formulae L-1to L-15 below, and T represents an alkyl group, a haloalkyl group, acyano group, a vinyl group, an ethynyl group, an aryl group, aheteroaryl group, an oxyethylene group, an oligooxyethylene group inwhich a repetition number of oxyethylene units is two or greater, asiloxane group, an oligosiloxane group having two or more silicon atoms,or a trialkylsilyl group, and

in Formulae L-1 to L-15, a wavy line portion represents a bondingposition to S or another divalent linking group represented by any oneof Formulae L-1 to L-15, * represents a bonding position to T or anotherdivalent linking group represented by any one of Formulae L-1 to L-15, min Formula L-13 represents an integer of 0 to 4, m's in Formulae L-14and L-15 each represent an integer of 0 to 2, R″s in Formulae L-1 andL-2 each independently represent a hydrogen atom or a substituent, andR″'s in Formulae L-13, L-14, and L-15 each independently represent asubstituent.
 2. The organic semiconductor element according to claim 1,wherein both of X¹ and X² are chalcogen atoms, or both of Y¹ and Y² arechalcogen atoms.
 3. The organic semiconductor element according to claim1, wherein Z is a hydrogen atom.
 4. The organic semiconductor elementaccording to claim 1, wherein p and q are each independently 1 or
 2. 5.The organic semiconductor element according to claim 1, wherein both ofp and q are
 1. 6. The organic semiconductor element according to claim5, wherein substitution positions of R¹ and R² are respectively secondpositions of terminal chalcogenophene rings.
 7. The organicsemiconductor element according to claim 1, wherein X^(a) is a S atom.8. The organic semiconductor element according to claim 1, wherein bothof two terminal chalcogenophene rings in Formula 1 are thiophene rings.9. The organic semiconductor element according to claim 1, wherein a sumof the numbers of carbon atoms in the group represented by Formula W is4 to
 40. 10. The organic semiconductor element according to claim 1,wherein L is a divalent linking group represented by any one of FormulaeL-1 to L-4 and L-13 to L-15, or a divalent linking group obtained bybonding two or more divalent linking groups represented by any one ofFormulae L-1 to L-4 and L-13 to L-15.
 11. The organic semiconductorelement according to claim 1, wherein L is a divalent linking grouprepresented by any one of Formulae L-1 to L-4 and L-13 to L-15 singly.12. The organic semiconductor element according to claim 1, wherein T isan alkyl group.
 13. The organic semiconductor element according to claim1, wherein W is an alkyl group.
 14. The organic semiconductor elementaccording to claim 1, which is an organic thin film transistor.
 15. Anorganic semiconductor composition comprising: a compound represented byFormula 1 below; and a solvent having a boiling point of 100° C. orhigher, wherein a content of the compound represented by Formula 1 is 20mass % or less with respect to a total amount of the organicsemiconductor composition,

in Formula 1, A represents a central aromatic ring and is an aromaticring selected from any one of aromatic rings represented by Formula 2 or3, *'s represent bonding positions to two side chalcogenophene rings,and X^(a)'s represent chalcogen atoms, one of X¹ and Y¹ is a chalcogenatom and the other is C(R^(a)), one of X² and Y² is a chalcogen atom andthe other is C(R^(b)), R^(a)'s each independently represent a hydrogenatom or R¹, R^(b)'s each independently represent a hydrogen atom or R²,in a case where A is an aromatic ring represented by Formula 3, Y¹ andY² are each independently a chalcogen atom, X¹ is C(R^(a)), and X² isC(R^(b)), p and q each independently represent an integer of 0 to 2, Z'seach independently represent a hydrogen atom or a halogen atom, and R¹and R² each independently represent a halogen atom or a grouprepresented by Formula W below,—S-L-T  (W) in Formula W, S represents a single bond or—(C(R^(S))₂)_(n)—, R^(S)'s each independently represent a hydrogen atomor a halogen atom, n represents an integer of 1 to 17, L represents asingle bond, a divalent linking group represented by any one of FormulaeL-1 to L-15 below, or a divalent linking group obtained by bonding twoor more divalent linking groups represented by any one of Formulae L-1to L-15 below, and T represents an alkyl group, a haloalkyl group, acyano group, a vinyl group, an ethynyl group, an aryl group, aheteroaryl group, an oxyethylene group, an oligooxyethylene group inwhich a repetition number of oxyethylene units is two or greater, asiloxane group, an oligosiloxane group having two or more silicon atoms,or a trialkylsilyl group, and

in Formulae L-1 to L-15, a wavy line portion represents a bondingposition to S or another divalent linking group represented by any oneof Formulae L-1 to L-15, * represents a bonding position to T or anotherdivalent linking group represented by any one of Formulae L-1 to L-15, min Formula L-13 represents an integer of 0 to 4, m's in Formulae L-14and L-15 each represent an integer of 0 to 2, R″s in Formulae L-1 andL-2 each independently represent a hydrogen atom or a substituent, andR″'s in Formulae L-13, L-14, and L-15 each independently represent asubstituent.
 16. The organic semiconductor composition according toclaim 15, further comprising: a binder polymer, wherein a content of thebinder polymer is 0.001 to 10 mass % with respect to a total amount ofthe organic semiconductor composition.
 17. A method of manufacturing anorganic semiconductor element, comprising: an applying step of applyingthe organic semiconductor composition according to claim 15 to asubstrate by an ink jet method or a flexographic printing method; and aremoving step of removing at least a portion of the solvent from theapplied organic semiconductor composition.
 18. An organic semiconductorfilm formed from the organic semiconductor composition according toclaim 15.